Formic acid (HCOOH) dimers are studied by infrared spectroscopy in a nitrogen matrix and by ab initio calculations. We benefit from the use of a nitrogen matrix where the lifetime of the higher-energy (cis) conformer is very long (∼11 h vs. 7 min in an argon matrix). As a result, in a nitrogen matrix, a large proportion of the cis conformer can be produced by vibrational excitation of the lower-energy (trans) conformer. Three trans-trans, four trans-cis, and three cis-cis dimers are found in the experiments. The spectroscopic information on most of these dimers is enriched compared to the previous studies in an argon matrix. The cis-cis dimers of ordinary formic acid (without deuteration) are reported here for the first time. Several conformational processes are obtained using selective excitation by infrared light, some of them also for the first time. In particular, we report on the formation of cis-cis dimers upon vibrational excitation of trans-cis dimers. Tunneling decays of several dimers have been detected in the dark. The tunneling decay of cis-cis dimers of formic acid as well as the stabilization of cis units in cis-cis dimers is also observed for the first time.
Skip Nav Destination
Article navigation
21 January 2018
Research Article|
January 17 2018
Formic acid dimers in a nitrogen matrix
Susy Lopes;
Susy Lopes
1
Department of Chemistry, University of Coimbra
, Rua Larga, P-3004-535 Coimbra, Portugal
Search for other works by this author on:
Rui Fausto
;
Rui Fausto
a)
1
Department of Chemistry, University of Coimbra
, Rua Larga, P-3004-535 Coimbra, Portugal
Search for other works by this author on:
Leonid Khriachtchev
Leonid Khriachtchev
a)
2
Department of Chemistry, University of Helsinki
, P.O. Box 55, FI-00014 Helsinki, Finland
Search for other works by this author on:
a)
Authors to whom correspondence should be addressed: leonid.khriachtchev@helsinki.fi and rfausto@ci.uc.pt
J. Chem. Phys. 148, 034301 (2018)
Article history
Received:
October 25 2017
Accepted:
January 02 2018
Citation
Susy Lopes, Rui Fausto, Leonid Khriachtchev; Formic acid dimers in a nitrogen matrix. J. Chem. Phys. 21 January 2018; 148 (3): 034301. https://doi.org/10.1063/1.5010417
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Pay-Per-View Access
$40.00
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
A theory of pitch for the hydrodynamic properties of molecules, helices, and achiral swimmers at low Reynolds number
Anderson D. S. Duraes, J. Daniel Gezelter
Electronic structure simulations in the cloud computing environment
Eric J. Bylaska, Ajay Panyala, et al.
Related Content
Acetic acid dimers in a nitrogen matrix: Observation of structures containing the higher-energy conformer
J. Chem. Phys. (September 2015)
Acetic acid–water complex: The first observation of structures containing the higher-energy acetic acid conformer
J. Chem. Phys. (February 2016)
Tetrazole acetic acid: Tautomers, conformers, and isomerization
J. Chem. Phys. (February 2014)
Formic and acetic acids in a nitrogen matrix: Enhanced stability of the higher-energy conformer
J. Chem. Phys. (October 2010)
Vibrational exciton coupling in homo and hetero dimers of carboxylic acids studied by linear infrared and Raman jet spectroscopy
J. Chem. Phys. (September 2018)