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• W2469109350 abstract "We have employed electron bombardment during matrix deposition of CO2 (or 13CO2, C18O2) and para-hydrogen (p-H2) at 3.2 K and recorded infrared (IR) spectra of t-HOCO+, H+(CO2)2, HCO2−, CO2−, t-HOCO, and other species isolated in solid p-H2. After the matrix was maintained in darkness for 13 h, intensities of absorption features of t-HOCO+ at 2403.5 (ν1), 2369.9 (ν2), 1018.1 (ν4), and 606.5 (ν6) cm−1 and those of H+(CO2)2 at 1341.1, 883.6, and 591.5 cm−1 decreased. Corresponding lines of isotopologues were observed when 13CO2 or C18O2 replaced CO2. In contrast, lines of HCO2− at 2522.4 (ν1), 1616.1 (ν5), 1327.9 (ν2), and 745.6 (ν3) cm−1 increased in intensity; corresponding lines of H13CO2− or HC18O2− were also observed. Lines of t-DOCO+ and DCO2− were observed in an electron bombarded CO2 /normal-deuterium (n-D2) matrix. Data of ν6 of t-HOCO+ and all observed modes of H18OC18O+ and HC18O2− 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 ν1 line of t-HOCO+ in solid p-H2 (2403.5 cm−1), similar to the line at 2673 cm−1 of t-HOCO+ tagged with an Ar atom, is significantly red-shifted from that reported for gaseous t-HOCO+ (3375.37 cm−1) due to partial proton sharing between CO2 and H2 or Ar. The ν1 line of HCO2− in solid p-H2 (2522.4 cm−1) is blue shifted from that reported for HCO2− in solid Ne (2455.7 cm−1) and that of HCO2− tagged with Ar (2449 cm−1); this can be explained by the varied solvation effects by Ne, Ar, or H2 on the mixing of H+ + CO2 and H + CO2− surfaces. Possible formation mechanisms of t-HOCO+, H+(CO2)2, HCO2−, CO2−, t-HOCO, H2O, and t-HCOOH are discussed." @default.
• W2469109350 created "2016-07-22" @default.
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• W2469109350 date "2016-07-05" @default.
• W2469109350 modified "2023-10-16" @default.
• W2469109350 title "Infrared absorption of t-HOCO+, H+(CO2)2, and HCO2− produced in electron bombardment of CO2 in solid para-H2" @default.
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• W2469109350 doi "https://doi.org/10.1063/1.4954898" @default.
• W2469109350 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/27394107" @default.
• W2469109350 hasPublicationYear "2016" @default.
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