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DOE OSTI2012

NVMalloc: Exposing an Aggregate SSD Store as a Memory Partition in Extreme-Scale Machines

DRAM is a precious resource in extreme-scale machines and is increasingly becoming scarce, mainly due to the growing number of cores per node. On future multi-petaflop and exaflop machines, the memory pressure is likely to be so severe that we need to rethink our memory usage models. Fortunately, the advent of non-volatile memory (NVM) offers a unique opportunity in this space. Current NVM offerings possess several desirable properties, such as low cost and power efficiency, but suffer from high latency and lifetime issues. We need rich techniques to be able to use them alongside DRAM. In this talk, we present a novel approach for exploiting NVM as a secondary memory partition so that applications can explicitly allocate and manipulate memory regions therein. More specifically, we propose an NVMalloc library with a suite of services that enables applications to access a distributed NVM storage system. We have devised ways within NVMalloc so that the storage system, built from compute node-local NVM devices, can be accessed in a byte-addressable fashion using the memory mapped I/O interface. Our approach has the potential to re-energize out-of-core computations on largescale machines by having applications allocate certain variables through NVMalloc, thereby increasing the overall memory capacity available. Our evaluation on a 128-core cluster shows that NVMalloc enables applications to compute problem sizes larger than the physical memory in a cost-effective manner. It can bring more performance/efficiency gain with increased computation time between NVM memory accesses or increased data access locality. In addition, our results suggest that while NVMalloc enables transparent access to NVM-resident variables, the explicit control it provides is crucial to optimize application performance.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2016

Speeding up equation of motion coupled cluster theory with the chain of spheres approximation

In the present paper, the chain of spheres exchange (COSX) approximation is applied to the highest scaling terms in the equation of motion (EOM) coupled cluster equations with single and double excitations, in particular, the terms involving integrals with four virtual labels. It is found that even the acceleration of this single term yields significant computational gains without compromising the desired accuracy of the method. For an excitation energy calculation on a cluster of five water molecules using 585 basis functions, the four virtual term is 9.4 times faster using COSX with a loose grid than using the canonical implementation, which yields a 2.6 fold acceleration for the whole of the EOM calculation. For electron attachment calculations, the four virtual term is 15 times and the total EOM calculation is 10 times faster than the canonical calculation for the same system. The accuracy of the new method was tested using Thiel’s test set for excited states using the same settings and the maximum absolute deviation over the whole test set was found to be 12.945 cm{sup −1} (59 μHartree) for excitation energies and 6.799 cm{sup −1} (31 μHartree) for electron attachments. Using MP2 amplitudes for the ground state in combination with the parallel evaluation of the full EOM equations in the manner discussed in this paper enabled us to perform calculations for large systems. Electron affinity values for the two lowest states of a Zn protoporphyrine model compound (224 correlated electrons and 1120 basis functions) were obtained in 3 days 19 h using 4 cores of a Xeon E5-2670 processor allocating 10 GB memory per core. Calculating the lowest two excitation energies for trans-retinal (114 correlated electrons and 539 basis functions) took 1 day 21 h using eight cores of the same processor and identical memory allocation per core.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Unveiling the Universe with emerging cosmological probes

The detection of the accelerated expansion of the Universe has been one of the major breakthroughs in modern cosmology. Several cosmological probes (Cosmic Microwave Background, Supernovae Type Ia, Baryon Acoustic Oscillations) have been studied in depth to better understand the nature of the mechanism driving this acceleration, and they are being currently pushed to their limits, obtaining remarkable constraints that allowed us to shape the standard cosmological model. In parallel to that, however, the percent precision achieved has recently revealed apparent tensions between measurements obtained from different methods. These are either indicating some unaccounted systematic effects, or are pointing toward new physics. Following the development of CMB, SNe, and BAO cosmology, it is critical to extend our selection of cosmological probes. Novel probes can be exploited to validate results, control or mitigate systematic effects, and, most importantly, to increase the accuracy and robustness of our results. This review is meant to provide a state-of-art benchmark of the latest advances in emerging “beyond-standard” cosmological probes. We present how several different methods can become a key resource for observational cosmology. In particular, we review cosmic chronometers, quasars, gamma-ray bursts, standard sirens, lensing time-delay with galaxies and clusters, cosmic voids, neutral hydrogen intensity mapping, surface brightness fluctuations, stellar ages of the oldest objects, secular redshift drift, and clustering of standard candles. The review describes the method, systematics, and results of each probe in a homogeneous way, giving the reader a clear picture of the available innovative methods that have been introduced in recent years and how to apply them. The review also discusses the potential synergies and complementarities between the various probes, exploring how they will contribute to the future of modern cosmology.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2024

Beam test performance studies of CMS Phase-2 Outer Tracker module prototypes

A new tracking detector will be installed as part of thePhase-2 upgrade of the CMS detector for the high-luminosity LHC era.This tracking detector includes the Inner Tracker, equipped withsilicon pixel sensor modules, and the Outer Tracker, consisting ofmodules with two parallel stacked silicon sensors. The Outer Trackerfront-end ASICs will be able to correlate hits from chargedparticles in these two sensors to perform on-module discriminationof transverse momenta (p$_{T}$). The p$_{T}$information is generated at a frequency of 40 MHz and will be usedin the Level-1 trigger decision of CMS. Prototypes of theso-called 2S modules were tested at the Test Beam Facility at DESYHamburg between 2019 and 2020. These modules use the finalfront-end ASIC, the CMS Binary Chip (CBC), and for the firsttime the Concentrator Integrated Circuit (CIC), optical readoutand on-module power conversion. In total, seven modules were tested,one of which was assembled with sensors irradiated with protons. Animportant aspect was to show that it is possible to read out modulessynchronously. A cluster hit efficiency of about 99.75 % wasachieved for all modules. The CBC p$_{T}$ discriminationmechanism has been verified to work together with the CIC andoptical readout. The measured module performance meets therequirements for operation in the upgraded CMS tracking detector.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2023

On the potentially transformative role of auxiliary-field quantum Monte Carlo in quantum chemistry: A highly accurate method for transition metals and beyond

Approximate solutions to the ab initio electronic structure problem have been a focus of theoretical and computational chemistry research for much of the past century, with the goal of predicting relevant energy differences to within “chemical accuracy” (1 kcal/mol). For small organic molecules, or in general, for weakly correlated main group chemistry, a hierarchy of single-reference wave function methods has been rigorously established, spanning perturbation theory and the coupled cluster (CC) formalism. For these systems, CC with singles, doubles, and perturbative triples is known to achieve chemical accuracy, albeit at O(N7) computational cost. In addition, a hierarchy of density functional approximations of increasing formal sophistication, known as Jacob’s ladder, has been shown to systematically reduce average errors over large datasets representing weakly correlated chemistry. However, the accuracy of such computational models is less clear in the increasingly important frontiers of chemical space including transition metals and f-block compounds, in which strong correlation can play an important role in reactivity. A stochastic method, phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC), has been shown to be capable of producing chemically accurate predictions even for challenging molecular systems beyond the main group, with relatively low O(N3 − N4) cost and near-perfect parallel efficiency. Herein, we present our perspectives on the past, present, and future of the ph-AFQMC method. We focus on its potential in transition metal quantum chemistry to be a highly accurate, systematically improvable method that can reliably probe strongly correlated systems in biology and chemical catalysis and provide reference thermochemical values (for future development of density functionals or interatomic potentials) when experiments are either noisy or absent. Finally, we discuss the present limitations of the method and where we expect near-term development to be most fruitful.

Chemistry↗

DOE OSTI2023

Multipoint Observations of Dispersive Scale Alfvénic Field‐Line Resonances Associated With Substorm Auroral Beads

We present a case study of the field-aligned current (FAC) systems that transpire within the high-altitude auroral acceleration region of an “auroral bead” initiated double oval substorm observed on 23 February 2001 by the Cluster fleet. Conjunctive Cluster measurements and auroral images from IMAGE reveal that auroral bead current system formation and evolution is a multi-scale, injection-mediated process. The FACs at large scales vary on substorm evolution time scales (~minutes) in response to the injection and evolution of hotter denser magnetospheric plasma. Embedded within the large-scale FACs are intense short-scale (≲ few 10s of km) currents comprising dispersive scale Alfvén wave (DAW) fluctuations. The DAWs are a complex mixture of ingoing and reflected components that regularly interfere to form a broad spectrum of kinetic (dispersive) scale Alfvénic field-line resonances (KFLRs). The Alfvénic currents appear as a nested series of upward and downward FAC densities with amplitudes reaching a few 100 nA/m 2 . Energized field-aligned or counterstreaming electrons near keV energies and below are observed with parallel skews that vary in concert with variations in the DAW current sense. Positive correlations between DAW electric field energy densities and the energies of energized H + , He + , and O + outflow are observed, indicative of ion energization within the DAW fields. Due to their L-shell location (L~5.8–7.0) and associations with injections, the KFLRs are interpreted as the high-altitude auroral zone analog of KFLRs observed in the equatorial inner magnetosphere.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2018

3-D Semantic Information Inference from Airborne Video. Final Report

We developed a full 3D modeling pipeline focusing on an important application scenario: city-scale 3D reconstruction from aerial imagery. We propose an approach to solve camera pose estimation and dense reconstruction from Wide Area Aerial Surveillance (WAAS) videos captured by an airborne platform. Our approach solves them in an online fashion: it incrementally updates a sparse 3D map and estimates the camera pose as each new frame arrives; depth maps of selected key frames are computed using a variational method and integrated to produce a full 3D model via volumetric reconstruction. In practice, aerial imagery is usually captured using a multicamera system. We propose an approach for camera pose estimation of multi-camera aerial imagery which is parallelized on multiple GPUs for efficiency. The approach is also extended for progressive 3D model acquisition with a hand-held camera. We also developed an offline approach since online approach is not a necessity and accuracy has higher priority over efficiency in many scenarios. We presented MeshRecon, a mesh-based offline system composed of three modules: a dense point cloud is generated using multi-resolution plane sweep method; an initial mesh model is extracted from the point cloud via global optimization considering visibility information of all images; the mesh model is then iteratively refined to capture structural details by optimizing the photometric consistency and spatial regularization. The major processes are parallelized on GPU for efficiency. For the aerial imagery case, we evaluate our system on several real-world multicamera aerial imagery datasets, each covering an urban scenario of several square kilometers. Quantitative result shows that the reconstructed geometric 3D model is highly accurate with error smaller than 1 meter over the entire city. Besides aerial imagery, we also evaluate its performance on general geometric 3D model acquisition of real-world objects. Result shows that the system is robust and flexible for various types of objects at different scales in both indoor and outdoor environments. Based on city 3D models reconstructed at different times, we present a system for city-scale geometry change detection by performing comparisons at the 3D geometry level. Our system is able to detect geometry changes at different scales, ranging from a building cluster to small-scale vegetation changes, with high accuracy.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2018

Fluctuation Dynamo in a Collisionless, Weakly Magnetized Plasma

Results from a numerical study of fluctuation dynamo in a collisionless, weakly magnetized plasma are presented. The key difference between this dynamo and its magnetohydrodynamic (MHD) counterpart is the adiabatic production of magnetic-field-aligned pressure anisotropy by the amplification of a weak seed field. This, in turn, drives kinetic instabilities on the ion-Larmor scale—namely, firehose and mirror—which sever the adiabatic link between the thermal and magnetic pressures, thereby allowing the dynamo to proceed. After an initial phase of rapid growth driven by these instabilities, the magnetic energy grows exponentially and exhibits a ${k}^{3/2}$ spectrum that peaks near the resistive scale, similar to the large-magnetic-Prandtl-number ($\mathrm{Pm}\gg 1$) MHD dynamo. The magnetic field self-organizes into a folded-sheet topology, with direction reversals at the resistive scale and field lines curved at the parallel scale of the flow. The effective $\mathrm{Pm}$ is determined by whether the ion-Larmor scale is above or below the field-reversing scale: in the former case, particles undergo Bohm-like diffusion; in the latter case, particles scatter primarily off of firehose fluctuations residing at the ends of the magnetic folds, and the viscosity becomes anisotropic. The magnetic field ultimately saturates at dynamical strengths, with its spectral peak migrating toward larger scales. This feature, along with an anti-correlation of magnetic-field strength and field-line curvature and a gradual thinning of magnetic sheets into ribbons, resembles the saturated state of the large-$\mathrm{Pm}$ dynamo, the primary differences manifesting in firehose/mirror-unstable regions. Furthermore, these results have implications for magnetic-field growth in the weakly collisional intracluster medium of galaxy clusters.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2016

A stringent limit on the amplitude of Alfvénic perturbations in high-beta low-collisionality plasmas

It is shown that low-collisionality plasmas cannot support linearly polarized shear-Alfvén fluctuations above a critical amplitude δB{sub ⊥}/B{sub 0}∼β{sup −1/2}, where β is the ratio of thermal to magnetic pressure. Above this cutoff, a developing fluctuation will generate a pressure anisotropy that is sufficient to destabilize itself through the parallel firehose instability. This causes the wave frequency to approach zero, interrupting the fluctuation before any oscillation. The magnetic field lines rapidly relax into a sequence of angular zig-zag structures. Such a restrictive bound on shear-Alfvén-wave amplitudes has far-reaching implications for the physics of magnetized turbulence in the high-β conditions prevalent in many astrophysical plasmas, as well as for the solar wind at ∼1 au where β ≳ 1.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2020

The completed SDSS-IV extended Baryon Oscillation Spectroscopic Survey: N -body mock challenge for the quasar sample

ABSTRACT The growth rate and expansion history of the Universe can be measured from large galaxy redshift surveys using the Alcock–Paczynski effect. We validate the Redshift Space Distortion models used in the final analysis of the Sloan Digital Sky Survey (SDSS) extended Baryon Oscillation Spectroscopic Survey (eBOSS) Data Release 16 quasar clustering sample, in configuration and Fourier space, using a series of halo occupation distribution mock catalogues generated using the OuterRim N-body simulation. We test three models on a series of non-blind mocks, in the OuterRim cosmology, and blind mocks, which have been rescaled to new cosmologies, and investigate the effects of redshift smearing and catastrophic redshifts. We find that for the non-blind mocks, the models are able to recover fσ8 to within 3 per cent and α∥ and α⊥ to within 1 per cent. The scatter in the measurements is larger for the blind mocks, due to the assumption of an incorrect fiducial cosmology. From this mock challenge, we find that all three models perform well, with similar systematic errors on fσ8, α∥, and α⊥ at the level of $\sigma _{f\sigma _8}=0.013$, $\sigma _{\alpha _\parallel }=0.012$, and $\sigma _{\alpha _\bot }=0.008$. The systematic error on the combined consensus is $\sigma _{f\sigma _8}=0.011$, $\sigma _{\alpha _\parallel }=0.008$, and $\sigma _{\alpha _\bot }=0.005$, which is used in the final DR16 analysis. For baryon acoustic oscillation fits in configuration and Fourier space, we take conservative systematic errors of $\sigma _{\alpha _\parallel }=0.010$ and $\sigma _{\alpha _\bot }=0.007$.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2016

Petascale Simulations of the Morphology and the Molecular Interface of Bulk Heterojunctions

Understanding how additives interact and segregate within bulk heterojunction (BHJ) thin films is critical for exercising control over structure at multiple length scales and delivering improvements in photovoltaic performance. The morphological evolution of poly(3-hexylthiophene) (P3HT) and phenyl-C 61 -butyric acid methyl ester (PCBM) blends that are commensurate with the size of a BHJ thin film is examined using petascale coarse-grained molecular dynamics simulations. When comparing 2 component and 3 component systems containing short P3HT chains as additives undergoing thermal annealing we demonstrate that the short chains alter the morphol- ogy in apparently useful ways: They efficiently migrate to the P3HT/PCBM interface, increasing the P3HT domain size and interfacial area. Simulation results agree with depth profiles determined from neutron reflectometry measurements that reveal PCBM enrichment near substrate and air interfaces, but a decrease in that PCBM enrich- ment when a small amount of short P3HT chains are integrated into the BHJ blend. Atomistic simulations of the P3HT/PCBM blend interfaces show a non-monotonic dependence of the interfacial thickness as a function of number of repeat units in the oligomeric P3HT additive, and the thiophene rings orient parallel to the interfacial plane as they approach the PCBM domain. Using the nanoscale geometries of the P3HT oligomers, LUMO and HOMO energy levels calculated by density functional theory are found to be invariant across the donor/acceptor interface. Finally, these connections between additives, processing, and morphology at all length scales are generally useful for efforts to improve device performance.

36 MATERIALS SCIENCE↗

DOE OSTI2022

AI4IO: A suite of AI-based tools for IO-aware scheduling

Traditional workload managers do not have the capacity to consider how IO contention can increase job runtime and even cause entire resource allocations to be wasted. Whether from bursts of IO demand or parallel file systems (PFS) performance degradation, IO contention must be identified and addressed to ensure maximum performance. In this paper, we present AI4IO (AI for IO), a suite of tools using AI methods to prevent and mitigate performance losses due to IO contention. AI4IO enables existing workload managers to become IO-aware. Currently, AI4IO consists of two tools: PRIONN and CanarIO. PRIONN predicts IO contention and empowers schedulers to prevent it. CanarIO mitigates the impact of IO contention when it does occur. We measure the effectiveness of AI4IO when integrated into Flux, a next-generation scheduler, for both small- and large-scale IO-intensive job workloads. Our results show that integrating AI4IO into Flux improves the workload makespan up to 6.4%, which can account for more than 18,000 node-h of saved resources per week on a production cluster in our large-scale workload.

Wyatt, II, Michael R.↗

DOE OSTI2012

Hardware Architectures for Data-Intensive Computing Problems: A Case Study for String Matching

DNA analysis is an emerging application of high performance bioinformatic. Modern sequencing machinery are able to provide, in few hours, large input streams of data, which needs to be matched against exponentially growing databases of known fragments. The ability to recognize these patterns effectively and fastly may allow extending the scale and the reach of the investigations performed by biology scientists. Aho-Corasick is an exact, multiple pattern matching algorithm often at the base of this application. High performance systems are a promising platform to accelerate this algorithm, which is computationally intensive but also inherently parallel. Nowadays, high performance systems also include heterogeneous processing elements, such as Graphic Processing Units (GPUs), to further accelerate parallel algorithms. Unfortunately, the Aho-Corasick algorithm exhibits large performance variability, depending on the size of the input streams, on the number of patterns to search and on the number of matches, and poses significant challenges on current high performance software and hardware implementations. An adequate mapping of the algorithm on the target architecture, coping with the limit of the underlining hardware, is required to reach the desired high throughputs. In this paper, we discuss the implementation of the Aho-Corasick algorithm for GPU-accelerated high performance systems. We present an optimized implementation of Aho-Corasick for GPUs and discuss its tradeoffs on the Tesla T10 and he new Tesla T20 (codename Fermi) GPUs. We then integrate the optimized GPU code, respectively, in a MPI-based and in a pthreads-based load balancer to enable execution of the algorithm on clusters and large sharedmemory multiprocessors (SMPs) accelerated with multiple GPUs.

Tumeo, Antonino↗

DOE OSTI2020

Anomalous thickness-dependent electrical conductivity in van der Waals layered transition metal halide, Nb 3 Cl 8

Understanding the electronic transport properties of layered, van der Waals transition metal halides (TMHs) and chalcogenides is a highly active research topic today. Of particular interest is the evolution of those properties with changing thickness as the 2D limit is approached. Here, we present the electrical conductivity of exfoliated single crystals of the TMH, cluster magnet, Nb 3 Cl 8 , over a wide range of thicknesses both with and without hexagonal boron nitride (hBN) encapsulation. The conductivity is found to increase by more than three orders of magnitude when the thickness is decreased from 280 µm to 5 nm, at 300 K. At low temperatures and below ~50 nm, the conductance becomes thickness independent, implying surface conduction is dominating. Temperature dependent conductivity measurements indicate Nb 3 Cl 8 is an insulator, however, the effective activation energy decreases from a bulk value of 310 meV to 140 meV by 5 nm. X-ray photoelectron spectroscopy (XPS) shows mild surface oxidation in devices without hBN capping, however, no significant difference in transport is observed when compared to the capped devices, implying the thickness dependent transport behavior is intrinsic to the material. A conduction mechanism comprised of a higher conductivity surface channel in parallel with a lower conductivity interlayer channel is discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2012

Solution to PDEs using radial basis function finite-differences (RBF-FD) on multiple GPUs

This paper presents parallelization strategies for the radial basis function-finite difference (RBF-FD) method. As a generalized finite differencing scheme, the RBF-FD method functions without the need for underlying meshes to structure nodes. It offers high-order accuracy approximation and scales as O(N) per time step, with N being with the total number of nodes. To our knowledge, this is the first implementation of the RBF-FD method to leverage GPU accelerators for the solution of PDEs. Additionally, this implementation is the first to span both multiple CPUs and multiple GPUs. OpenCL kernels target the GPUs and inter-processor communication and synchronization is managed by the Message Passing Interface (MPI). We verify our implementation of the RBF-FD method with two hyperbolic PDEs on the sphere, and demonstrate up to 9x speedup on a commodity GPU with unoptimized kernel implementations. On a high performance cluster, the method achieves up to 7x speedup for the maximum problem size of 27,556 nodes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2024

The evolution of model Rh/Fe 3 O 4 (001) catalysts in hydrogen environments

Single metal atoms dispersed on oxides are a new emerging class of catalysts owing to their unique electronic and chemical properties. Here, in this study, we have prepared a series of model single-atom catalysts possessing well-characterized Rh sites that include Rh adatoms (Rh ad ), mixed surface layers with octahedrally-coordinated Rh (Rh oct ), as well as metallic Rh clusters and nanoparticles (Rh met ) on Fe 3 O 4 (001). Using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), we investigated the activity of such model systems towards H2 and their stability in reducing environments. Our results show that the atomically dispersed Rhad and Rhoct species do not activate H 2 , which would result in the formation of surface hydroxyls on Fe 3 O 4 (001). In contrast, the presence of Rh met in H 2 results in the formation of hydroxyls and subsequent etching of the Fe 3 O 4 (001) at higher temperatures (≥ 500 K) due to water formation via the Mars-van Krevelen mechanism. Additionally, such surface etching leads to the release of the Rh oct from the surface lattice and their sintering to Rh met . To bridge the material gap between the surface science models and high surface area catalysts, we perform parallel studies on powder Rh/Fe 3 O 4 catalysts. The XPS characterization shows remarkable similarities between these systems. Further, our surface science studies provide an atomistic picture of the behavior of high surface area catalysts in the H 2 atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Intermolecular correlations of liquid and glassy CS 2 studied by synchrotron radiation x-ray diffraction

How is the orientation of molecular liquids ordered on cooling? What are the basic structures of molecular glasses, e.g., close to the crystalline structure or some special structures such as icosahedral cluster? These are long-standing questions in liquid and glass physics. Here, we have constructed a novel cryostat to prepare simple molecular glasses by vapor deposition and performed in situ synchrotron radiation x-ray diffraction experiments. The glassy state of a simple molecule CS 2 , which cannot be vitrified by normal liquid quenching, was successfully prepared with this instrument, and its diffraction data were collected in a wide Q-range of 0.16–25.7 Å -1 with a high-energy diffractometer at BL04B2, SPring-8. The diffraction data of liquid CS 2 were also recorded in a wide temperature range of 160–300 K. These diffraction data were analyzed with molecular dynamics simulations and reverse Monte Carlo modelings to investigate orientational correlation. From the obtained 3D structure models, the orientational correlation between neighboring CS 2 molecules was investigated quantitatively as a function of temperature. At room temperature, the parallel and T-shaped arrangements are preferred for the nearest neighbor correlation. On cooling, these arrangements are developed gradually, and its rate became prominent below the melting temperature (162 K). In the glassy state, the slipped-parallel arrangement is dominant as well as the T-shaped arrangement. Both arrangements appear in the CS 2 crystal, indicating that the structure of glassy CS 2 is close to that of crystalline CS 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

The elusive S{sub 2} state, the S{sub 1}/S{sub 2} splitting, and the excimer states of the benzene dimer

We observe the weak S{sub 0} → S{sub 2} transitions of the T-shaped benzene dimers (Bz){sub 2} and (Bz-d{sub 6}){sub 2} about 250 cm{sup −1} and 220 cm{sup −1} above their respective S{sub 0} → S{sub 1} electronic origins using two-color resonant two-photon ionization spectroscopy. Spin-component scaled (SCS) second-order approximate coupled-cluster (CC2) calculations predict that for the tipped T-shaped geometry, the S{sub 0} → S{sub 2} electronic oscillator strength f{sub el}(S{sub 2}) is ∼10 times smaller than f{sub el}(S{sub 1}) and the S{sub 2} state lies ∼240 cm{sup −1} above S{sub 1}, in excellent agreement with experiment. The S{sub 0} → S{sub 1} (ππ{sup ∗}) transition is mainly localized on the “stem” benzene, with a minor stem → cap charge-transfer contribution; the S{sub 0} → S{sub 2} transition is mainly localized on the “cap” benzene. The orbitals, electronic oscillator strengths f{sub el}(S{sub 1}) and f{sub el}(S{sub 2}), and transition frequencies depend strongly on the tipping angle ω between the two Bz moieties. The SCS-CC2 calculated S{sub 1} and S{sub 2} excitation energies at different T-shaped, stacked-parallel and parallel-displaced stationary points of the (Bz){sub 2} ground-state surface allow to construct approximate S{sub 1} and S{sub 2} potential energy surfaces and reveal their relation to the “excimer” states at the stacked-parallel geometry. The f{sub el}(S{sub 1}) and f{sub el}(S{sub 2}) transition dipole moments at the C{sub 2v}-symmetric T-shape, parallel-displaced and stacked-parallel geometries are either zero or ∼10 times smaller than at the tipped T-shaped geometry. This unusual property of the S{sub 0} → S{sub 1} and S{sub 0} → S{sub 2} transition-dipole moment surfaces of (Bz){sub 2} restricts its observation by electronic spectroscopy to the tipped and tilted T-shaped geometries; the other ground-state geometries are impossible or extremely difficult to observe. The S{sub 0} → S{sub 1}/S{sub 2} spectra of (Bz){sub 2} are compared to those of imidazole ⋅ (Bz){sub 2}, which has a rigid triangular structure with a tilted (Bz){sub 2} subunit. The S{sub 0} → S{sub 1}/ S{sub 2} transitions of imidazole-(benzene){sub 2} lie at similar energies as those of (Bz){sub 2}, confirming our assignment of the (Bz){sub 2} S{sub 0} → S{sub 2} transition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗