Spectroscopic study of energy transfer in collisions between vibrational excited H2 and CO2.

J Chem Phys

Xinjiang Key Laboratory of Solid State Physics and Devices, Xinjiang University, Urumqi 830017, China.

Published: December 2024


Category Ranking

98%

Total Visits

921

Avg Visit Duration

2 minutes

Citations

20

Article Abstract

The collisional energy transfer between vibrational excited H2(1, 7) and CO2 was investigated by exciting H2 to a vibrational excited state of v = 1, J = 7 by the stimulated Raman scattering technique. The coherent anti-Stokes Raman spectroscopy (CARS) technique determined that H2 was excited to the H2(1, 7) state. Varying the cuvette temperature, the number of H2(1, 7) particles was found to increase with the increase in H2 molar ratio α by scanning the intensity of the CARS spectrum, with peaks at different α at a temperature of 363 ± 15 K, but the peak temperature was not sensitive to α. Scanning CARS spectra after H2 collisions yielded that the energies of the excited states of H2 were mainly distributed in the vibrational and translational states, proving that the collisions between the excited states of H2 were linear collisions. The collisional transfer rate coefficients of H2(1, 7) and CO2 were obtained by fitting the Stern-Volmer equation as kv(H2) = (2.89 ± 0.30) × 10-13 cm3 s-1 and kv(CO2) = (8.23 ± 0.42) × 10-13 cm3 s-1. Exciting H2 to different states, it was found that the collisional transfer rate coefficient of CO2 was less affected by the energy of the vibrational excited H2. The rotational temperature was obtained from the Boltzmann distribution of the rotational dynamics, and it was found that the rotational temperature of CO2(0000, J) was about 3.4 times higher than that of CO2(0001, J), which proved that the energy of the vibrational excited H2 was mainly allocated to the higher rotational state of CO2(0000).

Download full-text PDF

Source
http://dx.doi.org/10.1063/5.0239602DOI Listing

Publication Analysis

Top Keywords

vibrational excited
20
energy transfer
8
excited
8
excited h21
8
h21 co2
8
excited states
8
collisional transfer
8
transfer rate
8
energy vibrational
8
rotational temperature
8

Similar Publications

Improved rotational characterization of the E3Σ1+(63S1) Rydberg state of CdAr van der Waals diatom: Excitation of single-isotopologue and J-level population distribution.

J Chem Phys

September 2025

Smoluchowski Institute of Physics, Faculty of Physics, Astronomy and Applied Computer Science, Jagiellonian University, Łojasiewicza 11, 30-348 Kraków, Poland.

An improved rotational characterization of the E3Σ1+(63S1) Rydberg state of the CdAr diatom produced in a supersonic beam and studied using laser induced fluorescence (LIF) excitation spectra is presented. As an example, the spectra of the E3Σ1+←A3Π0+(53P1) transition, originating from the excitation of a single 116Cd40Ar isotopologue, are recorded and analyzed. In the experiment, the optical-optical double resonance method is employed, utilizing the E3Σ1+(υ')←A3Π0+(53P1)(υ″=6)←X1Σ0+(υ=0) scheme.

View Article and Find Full Text PDF

A Subsystem Perspective on Vibrational Coupled Cluster Response Theory.

J Phys Chem A

September 2025

Deparment of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.

Based on a theoretical analysis of systems composed of subsystems described using a coupled cluster parametrization, we developed a vibrational coupled cluster embedding theory specifically tailored for the computation of response properties. This work identifies several strategies for calculating excitation energies, transition probabilities, and other response functions in large systems of interacting subsystems. A particularly effective embedding approach was formulated around a Lagrangian with multilinear interaction terms, yielding a structure that is nonlinear in both coupled cluster amplitudes and multipliers.

View Article and Find Full Text PDF

Visualizing Electronic Vibrations on the Wave Function Tiles of the Low-Lying Singlet Excited States of Benzene.

J Chem Theory Comput

September 2025

International Center for Quantum and Molecular Structures, Faculty of Physics, Shanghai University, Shanghai 200444, China.

The representation of the electronic structure of benzene is important for understanding the properties of planar and monocyclic organic carbon compounds. Resonant Kekulé and conjugated structures based on localized and delocalized electronic theories, respectively, can be used to depict the ground state of benzene; however, depictions of its electrons vibrating in the excited states remain to be clarified. This paper presents a novel algorithm for exploring the three lowest lying vertically singlet excited states of benzene, focusing on the electronic excitations between occupied π and unoccupied π* orbitals.

View Article and Find Full Text PDF

The coordination chemistry of the planar, doubly π-extended bipyridine analog, 6,6',7,7'-biphenanthridine (p-biphe), is presented. The phenanthridine units in p-biphe are fused together at the 6- and 7- positions, and the resulting rigid ligand is compared with the more flexible parent "biphe" fused only at the 6-positions. p-Biphe is intensely fluorescent in solution with a much higher quantum yield, but, unlike biphe, at 77 K the fluorescence is not accompanied by any significant phosphorescence.

View Article and Find Full Text PDF

Ionization of alkanes to form radical cations activates their otherwise unreactive C-H bonds, facilitating important chemical processes such as hydrocarbon cracking. This work investigates the radical cation dissociation dynamics of hexane (CH) structural isomers by using femtosecond time-resolved mass spectrometry and quantum chemical calculations. All five isomers exhibit competition between the yields of fragment ions arising from direct C-C bond cleavage or dissociative rearrangement with hydrogen migration on dynamical time scales of ∼50-300 fs, suggesting that hydrogen migration in the metastable cations operates on such short time scales.

View Article and Find Full Text PDF