Search NASA⌕ Search

SEARCH · Search NASA

Results for “1H”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Nanoscale modulation of flat bands via controllable charge density wave defects in 4⁢𝐻⁡𝑏−Ta⁢S 2

Electron correlation is a main driver of exotic quantum phases and their interplay. The 4H b-TaS 2 system, possessing an intrinsic heterostructure of 1T- and 1H -TaS 2 monolayers, offers a unique opportunity to control electron correlation by distorting the atomic lattice or tuning interlayer coupling. Here, we investigated intrinsically deformed charge-density waves (CDWs) in the 1T layer of 4H b-TaS 2 to elucidate and control their effects on flat bands using scanning tunneling microscopy and spectroscopy (STM/S) combined with first-principles calculations. We identified two types of CDW defects: Type 1 has structural distortion and locally suppressed flat bands, while Type 2 features an increased flat band filling factor of intact CDW structure. Density functional theory calculations indicate that a sulfur vacancy in the 1T layer distorts the CDW structure and gives rise to a Type 1, whereas a sulfur vacancy in the 1H layer reduces the interlayer charge transfer and leads to a Type 2. Furthermore, we demonstrated creating and erasing individual CDW defects via STM manipulation. Here, our findings provide a pathway to not only tune flat bands but also selectively manipulate the interaction between CDW, the atomic lattice, and interlayer coupling in strongly correlated systems with atomic precision.

Charge density waves↗
DOE OSTI2024

Extended Interacting Boson Model with Configuration Mixing Description For 98 Mo

An extended version of the interacting boson model (IBM), encompassing two-particle–two-hole (2p-2h) excitations originating from below a valence shell and one-particle–one-hole (1p-1h) excitations extending to the upper next-nearest major shell, is developed to investigate cross-shell excitation effects in the transitional nucleus 98 Mo. This extended IBM framework is utilized to reproduce experimentally observed properties such as low-lying positive-parity level energies, 𝐵⁡(𝐸⁢2) values, and the electric quadrupole moment of the 2$^{+}_{1}$ state, 𝜌 2 ⁡(𝐸⁢0, 0$^{+}_{2}$ → 0$^{+}_{g}$), as well as the strength functions of the isoscalar giant monopole resonance (ISGMR) and the isoscalar giant quadrupole resonance (ISGQR) in 98 Mo. It is shown that the extended consistent-𝑄 IBM, incorporating configuration mixing of both 2p-2h excitations from below the valence shell and 1p-1h excitations to the upper next-nearest major shell, describes the low-lying structural properties and the ISGMR and ISGQR strength distributions of 98 Mo quite well, with the ISGMR and the ISGQR strength distributions comparable to the results of the self-consistent quasiparticle random-phase approximation with Skyrme interactions.

90 ≤ A ≤ 149↗
DOE OSTI2020

Enhanced Component Performance Study: Turbine-Driven Pumps 1998–2018

This report presents an enhanced performance evaluation of turbine-driven pumps (TDPs) at U.S. commercial nuclear power plants. The data used in this study are based on the operating experience failure reports from calendar year 1998 through 2018 as reported in the Institute of Nuclear Power Operations (INPO) Consolidated Events Database (ICES). The TDP failure modes considered are failure to start (FTS), failure to run less than or equal to one hour (FTR≤1H), failure to run more than one hour (FTR>1H), and normally running systems FTS and failure to run (FTR). The component reliability estimates and the reliability data are trended for the most recent 10-year period while yearly estimates for reliability are provided for the entire study period. A highly statistically significant decreasing trend was identified in the standby TDP unavailability estimates.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2022

Additives in Localized High Concentration Electrolytes for Safe Lithium-Ion Batteries

In this work, the effects of various additives in a localized high concentration electrolyte (LHCE) on the cycling performance of lithium (Li)-ion batteries were studied. The LHCEs utilize trimethyl phosphate as a flame-retarding solvent and 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether as a medium-high flash point diluent, for the purpose to reduce the electrolyte flammability and improve the battery safety, which are not possessed by the conventional electrolytes of LiPF 6 in organic carbonates due to their high flammability. The LHCEs have unique solvation structure which enables the use of flame-retardant solvents to greatly decrease the electrolyte flammability as well as enhance the battery cycling stability. However, the additives added in the LHCEs result in different battery performances. The organic carbonate additives largely reduce the initial capacities although the cell capacity can be partially recovered with cycling. The two phosphate salt additives behave better than the organic carbonate additives in terms of cell capacity and cycling stability. More cell performance evaluation will be conducted and the detailed characterization will be performed to investigate the root causes of different behaviors of additives in the LHCEs on battery performances.

25 ENERGY STORAGE↗
DOE OSTI2026

Enhanced Component Performance Study: Motor Driven Pumps 1998-2024

This report presents an enhanced performance evaluation of motor-driven pumps (MDPs) at U.S. commercial nuclear power plants. The data used in this study are based on the operating experience failure reports from calendar year 1998 through 2024 as reported in the Institute of Nuclear Power Operations (INPO) Industry Reporting and Information System (IRIS). The MDP failure modes considered for standby systems are fail to start (FTS), fail to run (FTR) for one hour of operation (FTR=1H), FTR after one hour of operation (FTR>1H), and for normally running systems FTS and FTR. An eight-hour unreliability estimate is also calculated and trended. The component reliability estimates and the reliability data are trended for the most recent 10-year period while yearly estimates for reliability are provided for the entire study period.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2026

Enhanced Component Performance Study: Turbine-Driven Pumps 1998-2024

This report presents an enhanced performance evaluation of turbine driven pumps (TDPs) at U.S. commercial nuclear power plants. The data used in this study are based on the operating experience failure reports from calendar year 1998 through 2024 as reported in the Institute of Nuclear Power Operations (INPO) Industry Reporting and Information System (IRIS). The TDP failure modes considered for standby systems are fail to start (FTS), fail to run (FTR) for one hour of operation (FTR=1H), FTR after one hour of operation (FTR>1H), and for normally running systems FTS and FTR. An eight hour unreliability estimate is also calculated and trended. The component reliability estimates and the reliability data are trended for the most recent 10 year period while yearly estimates for reliability are provided for the entire study period. No increasing trends were identified for TDPs for the most recent 10 year period.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Two-dimensional heteronuclear single quantum coherence (HSQC) NMR spectra of lignin isolated from Populus trichocarpa residues after CELF pretreatment and CBP fermentation

Here we present a curated dataset of a series of two-dimensional heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra of lignin isolated from a woody energy crop (Populus trichocarpa) residues after co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment and consolidated bioprocessing (CBP) process. The natural poplar variant GW-9947 from the Center for Bioenergy Innovation (CBI) was used. The poplar was knife milled and passed through a 1 mm sieve. The CELF pretreatment was performed in a Parr autoclave reactor with 7.5 wt % solids loading, 0.5 wt% H2SO4 as catalyst at 150°C with 15, 25 and 30 minutes, respectively. Tetrahydrofuran was added in a 1:1 mass ratio with water as the pretreatment solvent. The residues from CELF pretreatment were then subjected to CBP using the bacterium C. thermocellum DSM 1313. CBP fermentations were performed at 60 °C in a shaker at 50 grams/L solids loadings. Lignin was isolated from the pretreated samples after ball-milling in a porcelain jar with ceramic balls via Retsch PM 200 at 580 rpm for 2.5 h followed by enzymatic hydrolysis in acetate buffer (pH 4.8, 50 °C) for 48 h. The lignin samples were characterized using 13C–1H HSQC experiments which were performed in a Bruker Avance III HD 500 MHz NMR spectrometer operating at a frequency of 125.12 MHz for the 13C nucleus. A standard Bruker pulse sequence was used on a Prodigy platform cryoprobe. The dry lignin samples were dissolved in deuterated dimethylsulfoxide for HSQC experiments. The spectra were acquired under the following acquisition conditions: 210 ppm spectral width in F1 (13C) dimension with 256 data points and 11 ppm spectral width in F2 (1H) dimension with 1024 data points, a 90° pulse, a one bond C–H coupling constant of 145 Hz, a 1.0 s pulse delay, and 64 scans. All the data was processed using the TopSpin 3.6 software (Bruker BioSpin). The NMR spectra provides structural characteristics information about lignin remaining in solids after CELF (150 °C with 15, 25 and 30 minutes) process and C. thermocellum CBP.

Lignin structure, HSQC, poplar, CELF, CBP, CBI↗
DOE OSTI2024

Two-dimensional heteronuclear single quantum coherence (HSQC) NMR spectra of lignin isolated from field grown transgenic poplar

Here we present a curated dataset of a series of two-dimensional heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra of lignin isolated from a field grown transgenic poplar engineered with a monolignol 4-O-methyltransferase (MOMT4). The poplar was collected from a 2-year-old rotation trees within a three-year field trial experiment. The poplar was Soxhlet-extracted with toluene/ethanol and the extractives-free poplar was then ball-milled in a Retsch PM100 planetary ball mill using a porcelain jar with ceramic balls at 600 rpm for 2 h (in 5 min on and 5 min off cycles to avoid excessive sample heating). The ball-milled materials were then subjected to enzymatic hydrolysis for 48 h followed by centrifugation and washing with deionized water. The solid residue was extracted twice with 96:4 (v/v) 1,4-dioxane/water mixture at room temperature overnight. The extracts were combined, rotary evaporated, and freeze-dried to recover the lignin. The dry lignin samples were dissolved in deuterated dimethyl sulfoxide for NMR experiments. 13C–1H HSQC experiments were performed in a Bruker Avance III HD 500 MHz NMR spectrometer operating at a frequency of 125.12 MHz for the 13C nucleus using a standard Bruker pulse sequence (hsqcetgpsisp2.2) on a Prodigy platform cryoprobe. The NMR spectra were acquired under the following acquisition conditions: 220 ppm spectral width in F1 (13C) dimension with 256 data points and 12 ppm spectral width in F2 (1H) dimension with 1024 data points, a 90° pulse, a one bond C–H coupling constant of 145 Hz, a 1.0 s pulse delay, and 64 scans. All the data was processed using the Bruker’s TopSpin 3.6 software. The NMR spectra provides structural characteristics information about lignin in field grown transgenic MOMT4 poplar. Additional meta data is embedded in the raw spectra figures.

Lignin structure, HSQC, poplar, field trial, MOMT4↗
DOE OSTI2024

Heteronuclear single quantum coherence (HSQC) NMR spectra of lignin isolated from switchgrass residues after fermentation with milling

Here we present a curated dataset of two-dimensional heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra of lignin isolated from a herbaceous energy crop (Panicum virgatum L.). The lowland variant “Timber” switchgrass from Ernst seeds was used. The switchgrass was knife milled and passed through a 2 mm sieve prior to consolidated bioprocessing (CBP) process. Switchgrass was suspended in Milli-Q water and autoclaved for 90 min on liquid cycles. The residues after autoclaving were then subjected to CBP using coculture of Clostridium thermocellum (C. thermocellum DSM 1313 (LL1004)) and Thermoanaerobacterium thermosaccarolyticum ( T. thermosaccharolyticum HG-8 ATCC 31960 (LL1244)). Once-fermented and twice-fermented (FF) switchgrass were subjected to ball and disc milling in bioreactors at 55 °C and 60, 48 grams/L solids loadings for primary and secondary fermentation respectively. When fermentations were completed, the residual solids were rinsed with milli-Q water. Lignin was isolated from the pretreated residues after ball-milling in a porcelain jar with ceramic balls via Retsch PM 200 at 600 rpm for 2 h followed by enzymatic hydrolysis in acetate buffer (pH 4.8, 50 °C) for 48 h. The dry lignin samples were dissolved in deuterated dimethyl sulfoxide (d6) and characterized using 13C–1H HSQC in a Bruker Avance III HD 500-MHz NMR spectrometer. A standard Bruker pulse sequence (hsqcetgpsisp.2) was used on a Prodigy platform cryoprobe. The spectra were acquired with the following acquisition conditions: 230 ppm spectral width in F1 (13C) dimension with 256 data points and 12 ppm spectral width in F2 (1H) dimension with 2048 data points, a 90° pulse, with a C–H coupling constant of 145 Hz, a 1.0 s pulse delay, and 64 scans. Spectra were processed using the Bruker TopSpin 3.6 software.

Lignin, HSQC, Switchgrass, CBP , Ball mill, Disc m↗
DOE OSTI2024

HSQC spectra of lignin isolated from poplar stems

Here we present a curated dataset of two-dimensional heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra of lignin isolated from stems of genetically engineered poplar through auxin signaling gene modification. The plants were grown in greenhouse with temperatures between 21 and 23 °C. Plants were harvested and the aboveground stems were cut off an approximately five-inch-long segment from the bottom end of the plant stem, debarked and air-dried for three weeks. The dried stem samples were Wiley milled (mesh size 20), Soxhlet-extracted with toluene/ethanol for 24 h to remove extractives. The extracted biomass was ball-milled in a Retsch PM100 planetary ball mill using a porcelain jar with ceramic balls at 600 rpm for 2 h (in 5 min on and 5 min off cycles to avoid excessive sample heating). The ball-milled materials were then subjected to enzymatic hydrolysis for 48 h followed by centrifugation and washing with deionized water. The solid residue was freeze-dried to recover the lignin. The dry stem lignin samples were dissolved in deuterated dimethyl sulfoxide (d6) and transferred into a 5 mm tube. 13C–1H HSQC experiments were performed in a Bruker Avance III HD 500 MHz NMR spectrometer operating at a frequency of 125.12 MHz for the 13C nucleus using a standard Bruker pulse sequence on a Prodigy platform cryoprobe. The NMR spectra were acquired under the following acquisition conditions: 230 ppm spectral width in F1 (13C) dimension with 256 data points and 12 ppm spectral width in F2 (1H) dimension with 2048 data points, a 90° pulse, a one bond C–H coupling constant of 145 Hz, a 1.0 s pulse delay, and 64 scans. Spectra were processed using the Bruker TopSpin 3.6 software. Additional meta data is embedded in the raw spectra figures.

HSQC, lignin, poplar, stems, CBI↗
DOE OSTI2024

HSQC spectra of lignin isolated from poplar roots

Here we present a curated dataset of two-dimensional heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra of lignin isolated from roots of a greenhouse grown natural population of an energy crop poplar (Populus trichocarpa). Dormant cuttings of field-grown poplar were grown in 6-liter pots in a peat-based media containing bark, perlite, vermiculite, dolomite lime and a wetting agent in an environmentally controlled greenhouse. Temperatures were between 21 and 23 °C, with supplemental lighting to support a 16-h day length using 1000-watt high-pressure sodium lights in greenhouse. Once established, all plants were cut-back, allowed to regrow and harvested at the same time following an eight-month long growth period. Plants were harvested and the belowground roots were washed off soils, blotted, dried in an oven at 70 °C for 3 days, and Wiley milled (mesh size 20). The roots were Soxhlet-extracted with toluene/ethanol for 24 h to remove extractives. The extracted roots were ball-milled in a Retsch PM100 planetary ball mill using a porcelain jar with ceramic balls at 600 rpm for 2 h (in 5 min on and 5 min off cycles to avoid excessive sample heating). The ball-milled materials were then subjected to enzymatic hydrolysis for 48 h followed by centrifugation and washing with deionized water. The solid residue was extracted twice with 96% (v/v) 1,4-dioxane/water mixture at room temperature overnight. The extracts were combined, rotary evaporated, and freeze-dried to recover lignin. The dry lignin samples were dissolved in deuterated dimethyl sulfoxide (d6) and transferred into a 5 mm tube. 13C–1H HSQC experiments were performed in a Bruker Avance III HD 500 MHz NMR spectrometer operating at a frequency of 125.12 MHz for the 13C nucleus using a standard Bruker pulse sequence on a Prodigy platform cryoprobe. The NMR spectra were acquired under the following acquisition conditions: 220 ppm spectral width in F1 (13C) dimension with 256 data points and 12 ppm spectral width in F2 (1H) dimension with 1024 data points, a 90° pulse, a one bond C–H coupling constant of 145 Hz, a 1.0 s pulse delay, and 64 scans. Spectra were processed using the Bruker TopSpin software. Additional meta data is embedded in the raw spectra figures.

HSQC, lignin, poplar, roots, CBI↗
DOE OSTI2026

Photochemically Triggered Para-Hydrogen-Induced Polarization in a Diplatinum Trihydride Complex

Transition metal complexes containing platinum(II) are of substantial interest for their rich photophysics, biomedical applications, and catalytic function. Nuclear magnetic resonance (NMR) spectra of the spin-1/2 isotope, 195Pt, offer detailed insights into the molecular structures of closed-shell Pt(II) complexes, including solvent effects. However, the sensitivity of 195Pt NMR is mediocre, and its NMR spectra are typically complex. As a result, 1H NMR spectra are used as the primary characterization tool for Pt(II)-based molecules, relying on J-coupling to the 195Pt nucleus to provide structural information from the resulting satellite peaks. In efforts to significantly improve the information content from 1H NMR spectroscopy in a Pt(II)-containing molecule, we utilize [Pt2H2(μ-H)(μ-dppm)2]PF6, where dppm is bis(diphenylphosphino)methane, and leverage its established photoactivity with UV light and H2 for para-hydrogen-induced polarization (PHIP) to enhance the resultant NMR signals, revealing numerous 195Pt J-couplings. Moreover, we investigate direct solvent hyperpolarization effects, as well as the indirect effects of solvent on the various observed J-coupling constants in the Pt species, demonstrating correlations with both Lewis basicity and dielectric constant.

Brown, Emily E. [Department of Chemistry; North Ca↗
NASA NTRS1977

Some results of the testing of a full-scale Ogee tip helicopter rotor; acoustics, loads, and performance

Full-scale tests were utilized to investigate the effect of the Ogee tip on helicopter rotor acoustics, performance, and loads. Two facilities were used for this study: the Langley whirl tower and a UH-1H helicopter. The test matrix for hover on the whirl tower involved thrust values from 0 to 44,480 N (10,000 lbs) at several tip Mach numbers for both standard and Ogee rotors. The full-scale testing on the UH-1H encompassed the major portion of the flight envelope for that aircraft. Both near-field acoustic measurements as well as far-field flyover data were obtained for both the Ogee and standard rotors. Data analysis of the whirl-tower test shows that the Ogee tip does significantly diffuse the tip vortex while providing some improvement in hover performance. Flight testing of both rotors indicates that the strong impulsive noise signature of the standard rotor can be reduced with the Ogee rotor. Forward flight performance was significantly improved with the Ogee configuration for a large number of flight conditions. Further, rotor control loads and vibrations were reduced through use of this advanced tip rotor.

Mantay, W. R.↗
NASA NTRS1978

Full-scale testing of an Ogee tip rotor

Full scale tests were utilized to investigate the effect of the ogee tip on helicopter rotor acoustics, performance, and loads. Two facilities were used: the Langley whirl tower and a UH-1H helicopter. The text matrix for hover on the whirl tower involved thrust values from 0 to 44 480 N (10,000 lb) at several tip Mach numbers for both standard and Ogee rotors. The full scale testing on the UH-1H encompassed the major portion of the flight envelope for that aircraft. Both near field acoustic measurements and far field flyover data were obtained for both the ogee and standard rotors. Data analysis of the whirl tower test shows that the ogee tip does significantly diffuse the tip vortex while providing some improvement in hover performance at low and moderate thrust coefficients. Flight testing of both rotors indicates that the strong impulsive noise signature of the standard rotor can be reduced with the ogee rotor. Analysis of the spectra indicates a reduction in energy in the 250 Hz and 1000 Hz range for the ogee rotor. Forward flight performance was significantly improved with the ogee configuration for a large number of flight conditions. Further, rotor control loads were reduced through use of this advanced tip rotor.

Mantay, W. R.↗
NASA NTRS1981

UGC 10683B - A possible X-ray emitting Seyfert galaxy

Optical spectra are presented for both members of the pair of interacting galaxies UGC 10683, lying close to the HEAO-A1 satellite's unidentified, high-altitude X-ray source 1H 1703-01. It is determined that one galaxy of the pair, UGC 10683B, is of Seyfert Type I, and it is suggested that it may be related to the X-ray source. Higher-resolution X-ray observations are deemed necessary to determine whether there is an identity between UGC 10683B and 1H 1703-01.

Wilson, A. S.↗
NASA NTRS1993

Aerospace devices for magnetic replicas

Retained persistent magnetic field has been studied and improved in the superconductor YBa2Cu3O7 (Y123). During the study, trapped magnetic field, B(t), has been increased by over a factor of 10(exp 5). Methods used to improve magnetic field trapping were principally: (1) the adoption of the Melt Texturing process to increase grain size; (2) the addition of excess Y to disperse deposits of Y2BaCuO5 (Y211) and again increase grain size; (3) irradiation with high energy particles including 1H+, 3He++, 4He++, and fission fragments; and (4) utilizing temperatures below 77 K has also been quantified as a way to increase trapped field. In addition, in our study of B(t), we have found laws governing creep, activation, temperature dependence, creep vs. current flow, etc. In the range 20 K less than or equal to T less than or equal to 65 K, and for B less than 10 Tesla, a simple empirical relationship was found: B(trap) (T2) = B(trap) (T1) ((Tc - T2)/(Tc - T1))squared where Tc is the critical temperature. The highest experimental trapped field was B(trap) = 3.96 Tesla, at 65 K. We believe this to be the highest persistent field ever produced, by any method. A two component model of the persistent currents has been developed. This accurately reproduces the data, using as parameters only the magnitude of a constant surface current, J(s), and a constant volume current J(v). The model successfully predicts B(t) (xyz) for the case of maximum trapped field, for all samples observed. It has also been extended to describe the unsaturated case either zero field cooled, or field cooled. Loss of strap with time has been studied for the critical state (Bt,max), and non critical state (Bt less than Bt,max), for times from a few minutes to a few months, for unirradiated material, for irradiation by 1H+, 3He++, 4He++, high z projectiles, and neutrons, and for all materials used in the overall study. We conclude that: (1) multi Tesla trapped fields are attained; (2) fields over 10 T are achievable; (3) creep is not a large problem; (4) application is feasible to motors, generators, magnets for particle beam optics, separators, levitating bearings, energy storage, shielding, and transportation.

Weinstein, Roy↗
NASA NTRS1994

SMM observations of gamma-ray transients. 3: A search for a broadened, redshifted positron annihilation line from the direction of the Galactic center

We have searched for 1980-1988 Solar Maximum Mission gamma-ray spectrometer data for transient emission on timescales from hours to approximately 12 days of broad gamma-ray lines at energies approximately 400 keV, which were reported by the High Energy Astronomy Observatory (HEAO) 1 and SIGMA experiments from two sources lying toward the Galactic center. The lines have been interpreted as the product of the annihilation of positrons in pair plasmas surrounding the black hole candidate 1E 1740.7-2942 and the X-ray binary 1H 1822-371. Our results from a combined exposure of approximately 1.5 x 10(exp 7)s provide no convincing evidence for transient emission of this line on any timescale between approximately 9 hr and approximately 1 yr. Our 3 sigma upper limits on the line flux during approximately 12 day intervals are characteristically 4.8 x 10(exp -3) photon/sq cm/s, while for approximately 1 day intervals our 3 sigma upper limits are characteristically 4.9 x 10(exp -3) photon/sq cm/s. These results imply a duty cycle of less than 1.3% for the transient line measured from 1H 1822-371 during a approximately 3 week interval in 1977 by HEAO 1, and a duty cycle of less than or = 0.8% for the transient line detected in 1990 and 1992 from 1E 1740.7-2942 on approximately 1 day timescales by SIGMA.

Harris, Michael J.↗
NASA NTRS2002

Effect of Electronic Excitation on Hydrogen Atom Transfer (Tautomerization) Reactions for the DNA Base Adenine

Geometrical structures and energetic properties for four different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest single excited state potential energy surface are studied. The energetic order of the tautomers on the ground state potential surface is 9H less than 7H less than 3H less than 1H, while on the excited state surface this order is found to be different: 3H less than 1H less than 9H less than 7H. Minimum energy reaction paths are obtained for hydrogen atom transfer (9 yields 3 tautomerization) reactions in the ground and the lowest excited electronic state. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic state, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. The barrier for this reaction in the excited state may become very low in the presence of water or other polar solvent molecules, and therefore such tautomerization reaction may play an important role in the solution phase photochemistry of adenine.

Chaban, Galina M.↗