Two-dimensional infrared spectroscopy from the gas to liquid phase: density dependent<i>J</i>-scrambling, vibrational relaxation, and the onset of liquid character

Pack, Greg Ng; Rotondaro, Matthew C.; Shah, Phalguni; Mandal, Aritra; Erramilli, Shyamsunder; Ziegler, L. D.

doi:10.1039/c9cp04101j

Cited by 14 publications

(16 citation statements)

References 79 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, we have discussed the influence of rotational coherence evolution during waiting time on the spectra and the conditions for collective destructive interference over whole 2D branches. Since most results apply to whole branches, we emphasize that the presented theory is also highly relevant for gas-phase 2DIR measurements that do not resolve individual lines, for example the recent work of Ziegler and co-workers [39,56], either because of insufficient resolution, high line density, or large pressure broadening. While simulations were performed on a simple diatomic molecule and a symmetric top molecule, our results are fully applicable to the more prevalent asymmetric tops.…”

Section: Discussionmentioning

confidence: 99%

Theory of rotationally resolved two-dimensional infrared spectroscopy including polarization dependence and rotational coherence dynamics

Kowzan,

Allison

2022

Preprint

View full text Add to dashboard Cite

Two-dimensional infrared (2DIR) spectroscopy is widely used to study molecular dynamics but it is typically restricted to optically thick samples and modest spectral resolution. The recently proposed technique of cavity-enhanced 2D spectroscopy using frequency combs and developments in multi-comb spectroscopy can lift these restrictions, demonstrating the need for rigorous and quantitative treatment of rotationally-resolved, polarization-dependent third-order response of gas-phase samples. This article provides such description using density-matrix, time-dependent perturbation theory and angular momentum algebra techniques. We describe the band and branch structure of 2D spectra, decompose the molecular response into polarization-dependence classes, use this decomposition to derive and explain special polarization conditions and relate the liquid-phase polarization conditions to gas-phase ones. Furthermore, we discuss the rotational coherence dynamics during waiting time.

show abstract

Section: Discussionmentioning

confidence: 99%

Theory of rotationally resolved two-dimensional infrared spectroscopy including polarization dependence and rotational coherence dynamics

Kowzan,

Allison

2022

Preprint

View full text Add to dashboard Cite

show abstract

“…However, IR study of fluids behavior and their liquid-like to gas-like state transitions are presented only in a few works to date. 5,6 Nevertheless, what has already been published is thought-*Corresponding author: grinwald@mts-nn.ru https://doi.org/10.2298/JSC210426048G…”

Section: Introductionmentioning

confidence: 99%

IR detection of the methane halides fluid-like state at ambient conditions

Гринвальд

Kapustin

2021

JSCS

View full text Add to dashboard Cite

The paper presents the IR-study of the fluid-like state generated at ambient conditions for methane halides (iodomethane, tetrachloromethane, tri-chloromethane, and dichloromethane). It was shown that at vapor compression-extension procedure realized in variable thickness spectral cell (VTOC), the dual phase state exhibiting both gas and liquid properties arises. A reversible transition from a gas-like to a liquid-like shape, independent on the thermodynamic characteristics of the studied methane halides, was revealed.

show abstract

“…While the dynamical aspects of energy migration are the main focus in electronic spectroscopy, the 2D spectroscopy approach in IR regime [31] has been utilized for molecular structure determination [2,32,33] and for tracking thermal fluctuations and chemical reaction dynamics [34][35][36][37] via vibrational resonances. Vibrational nonlinear spectroscopy allows direct measurement of diagonal and off-diagonal vibrational anharmonicities [38,39].…”

Section: Introductionmentioning

confidence: 99%

Revealing a full quantum ladder by nonlinear spectroscopy

Abramavičius¹

2020

Lith. J. Phys.

View full text Add to dashboard Cite

Coherent two-dimensional spectroscopy in the IR or the visible region is very effective for studying correlations, energy relaxation/transfer pathways in complex multi-chromophore or multi-mode systems. However, it is usually restricted up to two-quanta excitations and their properties. In this paper, an arbitrary level of excitation is suggested as the utility to scan nonlinear potential surfaces of quantum systems up to a desired excitation degree. This can be achieved by a simple three-pulse laser spectroscopy approach. Accurate evaluation of high-level anharmonicities as well as transition amplitudes can be directly obtained. Additionally, questions regarding the quantum nature of the probed system can be addressed by studying absolute peak positions.

show abstract

Two-dimensional infrared spectroscopy from the gas to liquid phase: density dependentJ-scrambling, vibrational relaxation, and the onset of liquid character

Abstract: Ultrafast 2DIR reveals rotational relaxation rates, critical slowing effects, and co-existence of free rotor and liquid populations in supercritical fluids.

Cited by 14 publications

References 79 publications

Theory of rotationally resolved two-dimensional infrared spectroscopy including polarization dependence and rotational coherence dynamics

Theory of rotationally resolved two-dimensional infrared spectroscopy including polarization dependence and rotational coherence dynamics

IR detection of the methane halides fluid-like state at ambient conditions

Revealing a full quantum ladder by nonlinear spectroscopy

Contact Info

Product

Resources

About