Polarization-angle-scanning two-dimensional spectroscopy: Application to dipeptide structure determination

Jun Ho Choi, Minhaeng Cho

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Coherent two-dimensional optical spectroscopy based on a heterodyne-detected stimulated photon echo measurement technique requires four ultrashort pulses whose pulse-to-pulse delay times, wavevectors, and frequencies are experimentally controllable variables. In addition, the polarization directions of the four radiations can also be arbitrarily adjusted. We show that the polarization-angle-scanning two-dimensional spectroscopy can be of effective use to selectively suppress either all the diagonal peaks or a cross-peak in a given two-dimensional spectrum. Theoretical relationships between the transition dipole vectors of a given pair of coupled modes or quantum transitions and the polarization angle configuration making the corresponding cross-peak vanish are established. Here, to shed light into the underlying principles of the polarization-angle-scanning two-dimensional spectroscopy, we considered the amide I vibrations of various isotope-labeled dipeptide conformers and show that one can selectively suppress a cross-peak by properly controlling the polarization angle of a chosen beam among them. Once the relative directions of the amide I transition dipole vectors are determined using the polarization-angle-scanning technique theoretically proposed here, they can serve as a set of constraints for determining structures of model peptides. The present work demonstrates that the polarization-controlled two-dimensional vibrational or electronic spectroscopy can provide invaluable information on intricate details of molecular structures.

Original languageEnglish
Pages (from-to)3766-3777
Number of pages12
JournalJournal of Physical Chemistry A
Volume115
Issue number16
DOIs
Publication statusPublished - 2011 Apr 28

Fingerprint

Dipeptides
Spectrum Analysis
Spectroscopy
Polarization
Scanning
scanning
polarization
Amides
spectroscopy
amides
Vibration
Molecular Structure
Photons
Laser pulses
Isotopes
pulses
dipoles
Radiation
Peptides
Ultrashort pulses

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Polarization-angle-scanning two-dimensional spectroscopy : Application to dipeptide structure determination. / Choi, Jun Ho; Cho, Minhaeng.

In: Journal of Physical Chemistry A, Vol. 115, No. 16, 28.04.2011, p. 3766-3777.

Research output: Contribution to journalArticle

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