Change search
ReferencesLink to record
Permanent link

Direct link
Significant Contributions of the Albrecht’s A Term to Nonresonant Raman Scattering Processes
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. Department of Chemical Physics, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui, China.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-3915-300X
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-3282-0711
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. Department of Chemical Physics, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui, China.ORCID iD: 0000-0003-0007-0394
2015 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 11, no 11, 5385-5390 p.Article in journal (Refereed) PublishedText
Abstract [en]

The Raman intensity can be well described by the famous Albrecht’s Raman theory that consists of A and B terms. It is well-known that the contribution from Albrecht’s A term can be neglected without any loss of accuracy for far-off resonant Raman scattering processes. However, as demonstrated in this study, we have found that this widely accepted long-standing assumption fails drastically for totally symmetric vibration modes of molecules in general off-resonant Raman scattering. Perturbed first-principles calculations for water molecule show that strong constructive interference between the A and B terms occurs for the Raman intensity of the symmetric O-H stretching mode, which can account for ∼40% of the total intensity. Meanwhile, a minor destructive interference is found for the angle bending mode. The state-to-state mapping between Albrecht’s theory and perturbation theory allows us to verify the accuracy of the widely employed perturbation method for the dynamic/resonant Raman intensities. The model calculations rationalized from water molecule with the bending mode show that the perturbation method is a good approximation only when the absolute energy difference between the first excited state and the incident light is more than five times greater than the vibrational energy in the ground state.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015. Vol. 11, no 11, 5385-5390 p.
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-181970DOI: 10.1021/acs.jctc.5b00761ISI: 000364614000031ScopusID: 2-s2.0-84946893555OAI: oai:DiVA.org:kth-181970DiVA: diva2:902917
Funder
Swedish Research Council
Note

QC 20160212

Available from: 2016-02-12 Created: 2016-02-11 Last updated: 2016-02-12Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Tian, GuangjunDuan, SaiLuo, Yi
By organisation
Theoretical Chemistry and Biology
In the same journal
Journal of Chemical Theory and Computation
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 19 hits
ReferencesLink to record
Permanent link

Direct link