Article
Chemistry, Physical
Rishabh Kumar Pandey, Korutla Srikanth, Anuj Tak, Abhishek Kumar, Tammineni Rajagopala Rao
Summary: This study focuses on the non-adiabatic effects in the photoelectron spectra of Al6N-. It performs ab initio electronic structure calculations for the first seven low-lying electronic states of Al6N- and conducts a nuclear dynamics study using time-dependent and time-independent quantum chemistry methods. A diabatic electronic representation is used to construct a model vibronic Hamiltonian and estimate the coupling parameters for the fifteen vibrational modes of Al6N-. Theoretical spectral bands are obtained using vibronic coupling theory and reduced dimensional calculations to understand the contribution of individual vibrational modes to the overall photoelectron spectra. The theoretically obtained photodetachment spectra show good agreement with the experimental spectra, indicating vibronic coupling between closely spaced spectral bands.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Chaoqun Zhang, Benjamin L. Augenbraun, Zack D. Lasner, Nathaniel B. Vilas, John M. Doyle, Lan Cheng
Summary: A generally applicable computational and experimental approach has been developed to determine vibronic branching ratios in linear polyatomic molecules to the 10(-5) level, showing improved sensitivity compared with previous methods. Knowledge of branching ratios at this level is crucial for the successful deep laser cooling of a broad range of molecular species.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Multidisciplinary Sciences
Enrico Ridente, Diptarka Hait, Eric A. Haugen, Andrew D. Ross, Daniel M. Neumark, Martin Head-Gordon, Stephen R. Leone
Summary: Understanding the relaxation pathways of photoexcited molecules is crucial for gaining atomistic-level insight into photochemistry. In this study, the geometric relaxation (Jahn-Teller distortion) of the methane cation was investigated using time-resolved attosecond transient absorption spectroscopy. The results revealed that the distortion occurred within a few femtoseconds after strong-field ionization of methane. Coherent oscillations in the vibrational mode of the symmetry-broken cation were activated and detected in the x-ray signal, but damped within a few tens of femtoseconds. This study provides a comprehensive understanding of the molecular relaxation dynamics and has implications for studying complex systems.
Article
Chemistry, Physical
V. M. Volokhov, L. V. Poluyanov
Summary: This study examines the relativistic pseudo-Jahn-Teller effect and Jahn-Teller effect using the microscopic (Breit-Pauli) spin-orbit coupling operator. The orbital and spin-orbital parts of the electronic Hamiltonian are expanded up to the second order terms in normal modes. Analytical forms of the five-dimensional (t2 +e) potential energy surfaces are obtained as functions of invariants of the Td group.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Chemistry, Physical
Minggang Guo, Zhifan Wang, Fan Wang
Summary: This study analyzed the structural characteristics of cyclic C3H3 using various computational methods and found that the structure with Cs symmetry is the only stable configuration, while other structures are second-order saddle points or transition states.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Review
Chemistry, Multidisciplinary
J. Patrick Zobel, Moritz Heindl, Felix Plasser, Sebastian Mai, Leticia Gonzalez
Summary: The simulation of photoinduced non-adiabatic dynamics is important in various scientific fields, and the challenges of solving the time-dependent molecular Schrodinger equation using MCTDH and SH methods need further research.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Materials Science, Multidisciplinary
El Habib Abbes, Hamza Abbassa, Said Meskine, Abdesamed Benbedra, Abdelkader Boukortt
Summary: In this study, the electronic and magnetic properties of Ni2MnGa Heusler alloy were investigated using Density Functional Theory. The focus was on the structural transition between tetragonal and cubic structures and its influencing factors. Results show that the tetragonal phase is the ground state for Ni2MnGa at 0K, with the alloy exhibiting double possibility of phase transition under thermal effect and uniaxial stress.
PHILOSOPHICAL MAGAZINE
(2022)
Article
Chemistry, Physical
Aleksandr G. Avramenko, Aaron S. Rury
Summary: This study investigates the formation of Herzberg-Teller vibronic polaritons through cavity polariton formation and a non-Condon vibronic coupling mechanism. Experimental evidence of HT polaritons is found in the light emission spectra of copper(II)tetraphenylporphyrin (CuTPP) molecules coupled to Fabry-Perot resonator structures. The enhancement of light emission from CuTPP and the temperature-dependent dispersion of the light emission peak energy are attributed to radiative relaxation into cavity photon states dressed by collective vibrations of the participating molecules. The complex interplay of electronic and nuclear degrees of freedom in light absorbing molecules can lead to a greater variety of coherent light-matter states, potentially transforming optoelectronic and photocatalytic technologies.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Gohil S. Thakur, Hans Reuter, Alexey V. Ushakov, Gianpiero Gallo, Juergen Nuss, Robert E. Dinnebier, Sergey V. Streltsov, Daniel I. Khomskii, Martin Jansen
Summary: The Jahn-Teller theorem is a fundamental concept in chemistry, where the distortion in local geometry is associated with a reduction of electronic energy. For Na9Bi5Os3O24, the heavily compressed octahedron around Os6+(5d(2)) results in a diamagnetic ground state, providing new insights in defining ground states of open shell electronic systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kishan Kumar Dakua, Karunamoy Rajak, Sabyashachi Mishra
Summary: The presence of excited electronic states near the optically bright state allows for various photo-relaxation channels. In transition-metal complexes, heavy atoms contribute to stronger spin-orbit coupling, enabling spin-forbidden processes to compete with spin-allowed processes. The distribution of these states is determined by the degree of vibronic coupling.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Review
Chemistry, Physical
Ketan Sharma, Terry A. Miller, John F. Stanton
Summary: This review focuses on the interaction of electronic and nuclear motion, known as vibronic coupling, in molecular dynamics and electronic spectroscopy. It explores how these effects are manifested in various spectra, with particular emphasis on fine-structure effects in Jahn-Teller systems. The review also provides insights into the quantum-mechanical origin of these splittings and computational strategies for predicting them.
INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shoma Hoshino, Kento Ishii, Koichi Tsukiyama
Summary: We investigated the predissociation dynamics of the Rydberg states of Br2 and found the existence of predissociation pathways through ion-pair states and core Rydberg states.
Article
Chemistry, Multidisciplinary
Bifeng Zhu, Zhuang Wu, Lina Wang, Bo Lu, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng
Summary: Efficient generation of the elusive trifluoromethylthiyl radical (CF3S) in gas phase through high-vacuum flash pyrolysis of bis(trifluoromethyl)disulfane oxide, followed by characterization and study in cryogenic matrixes. Additionally, observation of O2-oxidation via the novel thiylperoxy radical CF3SOO and photo-induced sulfur atom transfer (SAT) and isomerization.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Alexander S. Frolov, Carolien Callaert, Maria Batuk, Joke Hadermann, Andrey A. Volykhov, Anna P. Sirotina, Matteo Amati, Luca Gregoratti, Lada Yashina
Summary: This study investigates the reaction between the GeTe (111) surface with molecular oxygen, focusing on crystals with sole inversion domains. The reaction kinetics and structure of the oxide layer are evaluated, revealing nanoscale phase separation of GeO2 and Te, which is unusual for semiconductors.
Article
Chemistry, Physical
Swetha Erukala, Alexandra J. Feinberg, Cheol Joo Moon, Myong Yong Choi, Andrey F. Vilesov
Summary: Helium droplets are unique hosts for isolating molecular ions for spectroscopic experiments. This study shows that ion-molecule reactions in ethane are less efficient compared to ethylene, leading to the formation of weaker bound dimers and larger clusters.
JOURNAL OF CHEMICAL PHYSICS
(2022)