DOE OSTI2016
We have employed electron bombardment during matrix deposition of CO{sub 2} (or {sup 13}CO{sub 2}, C{sup 18}O{sub 2}) and para-hydrogen (p-H{sub 2}) at 3.2 K and recorded infrared (IR) spectra of t-HOCO{sup +}, H{sup +}(CO{sub 2}){sub 2}, HCO{sub 2}{sup −}, CO{sub 2}{sup −}, t-HOCO, and other species isolated in solid p-H{sub 2}. After the matrix was maintained in darkness for 13 h, intensities of absorption features of t-HOCO{sup +} at 2403.5 (ν{sub 1}), 2369.9 (ν{sub 2}), 1018.1 (ν{sub 4}), and 606.5 (ν{sub 6}) cm{sup −1} and those of H{sup +}(CO{sub 2}){sub 2} at 1341.1, 883.6, and 591.5 cm{sup −1} decreased. Corresponding lines of isotopologues were observed when {sup 13}CO{sub 2} or C{sup 18}O{sub 2} replaced CO{sub 2}. In contrast, lines of HCO{sub 2}{sup −} at 2522.4 (ν{sub 1}), 1616.1 (ν{sub 5}), 1327.9 (ν{sub 2}), and 745.6 (ν{sub 3}) cm{sup −1} increased in intensity; corresponding lines of H{sup 13}CO{sub 2}{sup −} or HC{sup 18}O{sub 2}{sup −} were also observed. Lines of t-DOCO{sup +} and DCO{sub 2}{sup −} were observed in an electron bombarded CO{sub 2} /normal-deuterium (n-D{sub 2}) matrix. Data of ν{sub 6} of t-HOCO{sup +} and all observed modes of H{sup 18}OC{sup 18}O{sup +} and HC{sup 18}O{sub 2}{sup −} are new. The assignments were made according to expected chemical behavior, observed isotopic shifts, and comparisons with vibrational wavenumbers and relative intensities of previous reports and calculations with the B3PW91/aug-cc-pVQZ method. The ν{sub 1} line of t-HOCO{sup +} in solid p-H{sub 2} (2403.5 cm{sup −1}), similar to the line at 2673 cm{sup −1} of t-HOCO{sup +} tagged with an Ar atom, is significantly red-shifted from that reported for gaseous t-HOCO{sup +} (3375.37 cm{sup −1}) due to partial proton sharing between CO{sub 2} and H{sub 2} or Ar. The ν{sub 1} line of HCO{sub 2}{sup −} in solid p-H{sub 2} (2522.4 cm{sup −1}) is blue shifted from that reported for HCO{sub 2}{sup −} in solid Ne (2455.7 cm{sup −1}) and that of HCO{sub 2}{sup −} tagged with Ar (2449 cm{sup −1}); this can be explained by the varied solvation effects by Ne, Ar, or H{sub 2} on the mixing of H{sup +} + CO{sub 2} and H + CO{sub 2}{sup −} surfaces. Possible formation mechanisms of t-HOCO{sup +}, H{sup +}(CO{sub 2}){sub 2}, HCO{sub 2}{sup −}, CO{sub 2}{sup −}, t-HOCO, H{sub 2}O, and t-HCOOH are discussed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗