Cis→trans conversion of formic acid by dissipative tunneling in solid rare gases:: Influence of environment on the tunneling rate

被引:159
作者
Pettersson, M
Maçoas, EMS
Khriachtchev, L
Lundell, J
Fausto, R
Räsänen, M
机构
[1] Univ Helsinki, Phys Chem Lab, FIN-00014 Helsinki, Finland
[2] Univ Coimbra, Dept Chem CQC, P-3004535 Coimbra, Portugal
关键词
D O I
10.1063/1.1521429
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The relaxation of the higher-energy cis conformer of formic acid to the lower-energy trans form by a tunneling mechanism has been investigated in low-temperature rare gas matrices. In the temperature range 8-60 K, the tunneling takes place dominantly from the vibrational ground state of the cis form and the temperature dependence of the tunneling rate constant is influenced by the interactions with the environment. The temperature-dependent tunneling rates for HCOOH and DCOOH in solid Ar, Kr, and Xe are measured including data for molecules in different local environments within each host. It was found that the medium and the local environment has a significant influence on the tunneling rate. (C) 2002 American Institute of Physics.
引用
收藏
页码:9095 / 9098
页数:4
相关论文
共 21 条
[1]   KETO-ENOL TAUTOMERIZATION OF 2-(2'-HYDROXYPHENYL)BENZOXAZOLE AND 2-(2'-HYDROXY-4'-METHYLPHENYL)BENZOXAZOLE IN THE TRIPLET-STATE - HYDROGEN TUNNELING AND ISOTOPE EFFECTS .1. TRANSIENT ABSORPTION KINETICS [J].
ALSOUFI, W ;
GRELLMANN, KH ;
NICKEL, B .
JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (25) :10503-10509
[2]  
[Anonymous], 1973, VIBRATIONAL SPECTROS
[3]   The low-temperature reactive tunneling in condensed phase. II. Multidimensional transition model [J].
Basilevsky, MV ;
Davidovitch, GV .
JOURNAL OF CHEMICAL PHYSICS, 2001, 115 (13) :6083-6094
[4]  
Bell R. P., 1980, TUNNEL EFFECT CHEM
[5]  
BENDERSKII V, 1994, CHEM DYNAMICS LOW TE
[6]  
BRUNTON G, 1978, J AM CHEM SOC, V100, P4197, DOI 10.1021/ja00481a031
[7]  
Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V16, P01
[8]   THE DECARBOXYLATION AND DEHYDRATION REACTIONS OF MONOMERIC FORMIC-ACID [J].
GODDARD, JD ;
YAMAGUCHI, Y ;
SCHAEFER, HF .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (02) :1158-1166
[9]   KINETIC STUDY OF HYDROGEN TUNNELLING IN MESO-TETRAPHENYLPORPHINE BY NUCLEAR MAGNETIC-RESONANCE LINESHAPE ANALYSIS AND SELECTIVE T1-RHO-RELAXATION TIME MEASUREMENTS [J].
HENNING, J ;
LIMBACH, HH .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1979, 75 :752-766
[10]   OTHER ROTAMER OF FORMIC-ACID, CIS-HCOOH [J].
HOCKING, WH .
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION A-A JOURNAL OF PHYSICAL SCIENCES, 1976, 31 (09) :1113-1121