Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/101236
Title: | Effects of Entangled IR Radiation and Tunneling on the Conformational Interconversion of 2-Cyanophenol | Authors: | Jesus, A. J. Lopes Nunes, Cláudio M. Reva, Igor Pinto, Sandra M V Fausto, Rui |
Issue Date: | 23-May-2019 | Publisher: | American Chemical Society | Project: | info:eu-repo/grantAgreement/POCI-01-0145-FEDER-028973/PT info:eu-repo/grantAgreement/FCT/UID/QUI/0313/2019 |
Serial title, monograph or event: | The Journal of Physical Chemistry A | Volume: | 123 | Issue: | 20 | Abstract: | The conformers of 2-cyanophenol (2CP) and their interconversions were studied by infrared (IR) spectroscopy after trapping the monomers of the gaseous compound into low-temperature (15 K) argon (Ar) and nitrogen (N2) matrixes. To assist in the interpretation of the experimental results, B3LYP, MP2, and QCISD electronic structure calculations were carried out for the 2CP molecule. Two planar conformers, cis and trans (orientation of OH with respect to the cyano group), are predicted with gas-phase populations at the sublimation temperature of ∼98 and ∼2%, respectively. The most stable form (cis) was experimentally identified in both cryomatrixes, whereas the less stable one (trans) was not detected in Ar but could be observed in the N2 matrix with an abundance of ∼15%. Selective and bidirectional conversion between the two identified conformers was achieved upon irradiating the compound trapped in N2 matrix with near-infrared (NIR) laser light tuned at the wavenumbers of the 2ν(OH) transitions of the respective conformers. The conformational composition of 2CP was also found to be affected by the broad-band IR radiation emitted by the spectrometer source. This effect could be suppressed, partially or completely, by using different long-pass IR filters, with cutoff values of approximately 2200, 1590, and 1170 cm-1. The observed conformational changes are rationalized in terms of a competition between the over-the-barrier (light-induced) and through-the-barrier (hydrogen atom tunneling) effects. Very interestingly, both effects occur on the same time scale. | URI: | https://hdl.handle.net/10316/101236 | ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/acs.jpca.9b01382 | Rights: | embargoedAccess |
Appears in Collections: | I&D CQC - Artigos em Revistas Internacionais |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
JPCA_2019-123-4396.pdf | 947.43 kB | Adobe PDF | View/Open |
SCOPUSTM
Citations
18
checked on Nov 17, 2022
WEB OF SCIENCETM
Citations
18
checked on May 2, 2023
Page view(s)
115
checked on Oct 9, 2024
Download(s)
106
checked on Oct 9, 2024
Google ScholarTM
Check
Altmetric
Altmetric
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.