Infrared Spectra of trans-HOCO, HCOOH+, and HCO2- Trapped in Solid Neon

Published

November 1, 2003

Author(s)

D Forney, Marilyn E. Jacox, Warren E. Thompson

Abstract

When a Ne: HCOOH sample is codeposited at ca. 5 K with neon atoms that have been passed through a microwave discharge, new absorptions appear in the infrared spectrum of the resulting solid which can be assigned to trans-HOCO, trans-HCOOH⁺, and HCO₂^-. The absorptions of trans-HOCO are readily identified by comparison with those previously reported for that molecule trapped in solid argon. Preliminary assignments of infrared absorptions of HOCO⁺, confirmed in studies using another experimental system, are also suggested. The identifications of trans-HCOOH⁺ and of HCO₂^- are aided by study of the photo destruction characteristics of these products when the deposit is exposed to various wavelengths of visible and ultraviolet radiation, by analysis of the spectra obtained from isotopically substituted samples, and by comparison with the results of ab initio and density functional calculations. Three previously unidentified vibrational fundamentals of trans-HCOOH⁺ have been assigned, as have been four vibrational fundamentals of HCO₂^- in the inert, nonionic environment of solid neon. The CH-stretching fundamental of HCO₂^- appears at an exceptionally low frequency. The results of density functional calculations of the structures and vibrational fundamentals of trans-HCOOH⁼HCO₂^-, the W(C_2v) structure of C(OH)₂⁺, and cis- and trans-HCOOH^- are given.

Citation

Journal of Chemical Physics

Volume

119

Issue

No. 20

Pub Type

Journals

Keywords

C(OH)₂⁺, density functional calculation, HCO₂, HCOOH, HCOOH, HCOOH⁺, infrared spectrum, neon matrix, trans-HOCO

Citation

Forney, D. , Jacox, M. and Thompson, W. (2003), Infrared Spectra of trans-HOCO, HCOOH⁺, and HCO₂^- Trapped in Solid Neon, Journal of Chemical Physics (Accessed April 19, 2024)