Article
Chemistry, Physical
Maitreyee Sharma Priyadarshini, Sung Min Jo, Simone Venturi, David W. Schwenke, Richard L. Jaffe, Marco Panesi
Summary: Understanding the kinetics of the HCN system is crucial in various scientific and engineering disciplines. This paper presents a rovibrational state-specific kinetic mechanism for the HCN system, using electronic structure calculations, classical scattering dynamics, and state-to-state kinetics. The study reveals that the dissociation of molecules in the HCN system is primarily controlled by potential energy surfaces (PESs) through the formation of short-lived intermediates. The exchange processes in CH and NH significantly enhance the dissociation by over 80%.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Maitreyee Sharma Priyadarshini, Sung Min Jo, Simone Venturi, David W. Schwenke, Richard L. Jaffe, Marco Panesi
Summary: Understanding the kinetics of the HCN system is critical to various disciplines, and this study provides insights into the rovibrational dynamics of dissociation in the HCN system by constructing a state-specific kinetic mechanism. The study highlights the role of potential energy surfaces in controlling the dissociation pathway, as well as the enhancing effect of exchange processes in CH and NH molecules on the dissociation reaction rate.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Mahsa Nazemi Ashani, Qinan Huang, A. Mackenzie Flowers, Alex Brown, Antoine Aerts, Alberto Otero-de-la-Roza, Gino A. Dilabio
Summary: The β-density functional theory (β-DFT) approach based on atom-centered potentials (ACPs) is shown to be a computationally inexpensive and accurate method for representing potential energy surfaces (PESs) and calculating vibrational frequencies for HONO and HFCO molecules. The ACP-corrected PESs produce small mean absolute errors and compared favorably to the results obtained with higher level of theory. This approach shows promise for representing accurate molecular PESs and calculating molecular properties.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Carmen Baiano, Jacopo Lupi, Vincenzo Barone, Nicola Tasinato
Summary: In this study, the isomerization of hydrogen cyanide on icy grain surfaces was investigated using a composite method (jun-Cheap) and density functional approaches. The results showed that four water molecules were involved in a proton relay mechanism, leading to a reduction in activation energy and facilitating the isomerization process.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Moritz Schneider, Daniel Born, Johannes Kaestner, Guntram Rauhut
Summary: The positions of grid points have a significant impact on the accuracy and computational effort of a multidimensional potential energy surface (PES) represented by n-mode expansions. Six different positioning schemes were studied, including a static approach and five adaptive schemes based on Gaussian process regression. Comparison with a more sophisticated approach by Christiansen et al. was made. The impact of grid point positions on multilevel PESs was discussed with respect to computational effort.
JOURNAL OF CHEMICAL PHYSICS
(2023)
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
Kai Topfer, Silvan Kaser, Markus Meuwly
Summary: This study investigates the mechanism of double proton transfer reaction in hydrated formic acid dimer at molecular level. The results reveal that temperature and solvent effects have a significant impact on the rate and competition process of the reaction, which is attributed to the subtle interplay between structural and electrostatic factors.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Physics, Multidisciplinary
Yang Huang, Michael Widom
Summary: This study investigates the vibrational entropy of a solid at finite temperature from the perspective of information theory. By using ab initio molecular dynamics simulations, the N-body distribution of atomic displacements at finite temperature is obtained, and the information-theoretic entropy is calculated. The results show good agreement with experimental values and the method is applicable to complex solids and cases where the quasiharmonic approximation fails.
Article
Chemistry, Physical
Kohei Tada, Hiroyuki Ozaki, Koji Fujimaru, Yasutaka Kitagawa, Takashi Kawakami, Mitsutaka Okumura
Summary: The study found that surface interactions can tune chemical indices and that weak adsorption onto ionic solids with charge-dipole interactions can enhance diradical character.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Emily K. Hockey, Korina Vlahos, Thomas Howard, Jessica Palko, Leah G. Dodson
Summary: The matrix-isolated infrared spectrum of a HCN-CH3Cl complex in a solid argon matrix was investigated using experimental and computational methods. The results suggest that the formation of the complex is promoted by the interaction of hydrogen and halogen bonds, providing insights into the search for life in space.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Ilya S. Sosulin, Mariia A. Lukianova, Anastasia D. Volosatova, Vladimir D. Drabkin, Svetlana V. Kameneva
Summary: Hydrogen bonding between saturated alkanes and HX is a unique type of interaction. Experimental and ab initio studies on the HCN...C2H6 complex show that only one structure is stabilized under experimental conditions, in good agreement with previous rotational spectroscopy studies.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Physical
Herve Tajouo Tela, Ernesto Quintas-Sanchez, Marie-Lise Dubernet, Yohann Scribano, Richard Dawes, Fabien Gatti, Steve Ndengue
Summary: In this study, the rovibrational states of the H2O-HCN van der Waals complex were calculated using a reliable quantum dynamical approach. The MCTDH approach was proposed as a reliable option for computing and characterizing rovibrational states of van der Waals complexes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Dong Liu, Rui Li, Juan Ren, Yongjun Cheng, Bing Yan, Yong Wu, Jian Guo Wang, Song Bin Zhang
Summary: This study investigates the electronic structures of diatomic dications, specifically focusing on dication HF2+, achieving good agreement with available references. In addition to common physical quantities, nonadiabatic radial coupling and diabatic potentials are presented. Further examination of predissociation states and shape resonances in collisions is conducted using WKB and scattering methods.
Article
Chemistry, Physical
Feina Zhai, Yun Tian, Dandan Song, Yuanjie Li, Xiaojing Liu, Ting Li, Zhaojun Zhang, Xiangjian Shen
Summary: An in-depth understanding of the interactions between hydrogen and transition metal catalysts is crucial for exploring novel heterogeneous hydrogenation reaction mechanisms. This study comprehensively investigates the interactions of hydrogen on active metal surfaces, revealing differences between Ni-group and Cu-group transition metals and the effects of reaction temperature and hydrogen partial pressure on stable adsorption phase diagrams. Additionally, the evolution of metal nanoparticles under moderate reaction conditions differs between Ni-group and Cu-group metals.
APPLIED SURFACE SCIENCE
(2021)
Review
Chemistry, Multidisciplinary
Edward Ditler, Sandra Luber
Summary: Vibrational spectroscopy is an important experimental technique for characterizing molecules and materials, but the interpretation of experimental results can be challenging. Computational studies using molecular dynamics simulations provide a valuable tool for understanding and predicting experimental results. This review article summarizes the field of vibrational spectroscopy using first-principles molecular dynamics and highlights recent advances in simulation techniques.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2022)
Article
Chemistry, Physical
Ernesto Quintas-Sanchez, Richard Dawes, Kelvin Lee, Michael C. McCarthy
JOURNAL OF PHYSICAL CHEMISTRY A
(2020)
Article
Chemistry, Physical
Dongzheng Yang, Junxiang Zuo, Jing Huang, Xixi Hu, Richard Dawes, Daiqian Xie, Hua Guo
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2020)
Article
Multidisciplinary Sciences
Shanyu Han, Carolyn E. Gunthardt, Richard Dawes, Daiqian Xie, Simon W. North, Hua Guo
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2020)
Article
Astronomy & Astrophysics
Benjamin Desrousseaux, Francois Lique, Javier R. Goicoechea, Ernesto Quintas-Sanchez, Richard Dawes
Summary: Detection of CF+ in interstellar clouds allows astronomers to infer elemental fluorine abundance and ionization fraction, requiring accurate determination through non-LTE excitation modeling. Quantum calculations of rotational excitation rate coefficients and non-LTE excitation models reveal population inversion in typical ISM photodissociation regions, successfully applied to fit CF+ emission lines observed in PDRs. Radiative transfer models with these new rate coefficients enable CF+ to be used as a powerful probe for studying molecular clouds exposed to strong stellar radiation fields.
ASTRONOMY & ASTROPHYSICS
(2021)
Article
Chemistry, Physical
Benjamin Desrousseaux, Ernesto Quintas-Sanchez, Richard Dawes, Sarantos Marinakis, Francois Lique
Summary: The rotational excitation of interstellar PN molecules induced by collisions with H-2 was investigated using a new ab initio four-dimensional potential energy surface (PES) for the PN-H-2 van der Waals system. The complex was found to have a linear equilibrium structure with specific separations and well-depths, and the integral cross sections for rotational excitation were strongly dependent on the rotational level of the H-2 molecule. These new collisional data are important for estimating PN abundance in the interstellar medium based on observational spectra.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Astronomy & Astrophysics
Cheikh T. Bop, Francois Lique, Alexandre Faure, Ernesto Quintas-Sanchez, Richard Dawes
Summary: This study investigated the rotational transition rate coefficients of HC2NC and HNC3, important for the spectra of cyanoacetylene isomers, and found significant differences in the rate coefficients for different translation reactions at different temperatures, which could lead to errors in excitation temperatures.
MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY
(2021)
Review
Chemistry, Physical
Ernesto Quintas-Sanchez, Richard Dawes
Summary: The Born-Oppenheimer potential energy surface (PES) has made significant progress in both conceptual understanding and practical applications since the 1920s. However, rigorous scattering calculations for complex molecules like the water dimer (H2O)2 continue to pose a challenge. Recent developments in approximate methodologies have shown promise in overcoming these challenges.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 72
(2021)
Article
Chemistry, Physical
Steve Ndengue, Ernesto Quintas-Sanchez, Richard Dawes, David Osborn
Summary: In this study, the electronic structure of nitrogen dioxide and its various molecular states were analyzed, with a focus on the low-lying vibrational levels on the ground state. Potential energy surfaces were fit and properties-based diabatization procedures were applied to produce accurate energies and couplings. The calculated electronic spectrum was in good agreement with experimental measurements, reproducing detailed structure with high accuracy and no empirical adjustments.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Physical
Shanyu Han, Ge Sun, Xianfeng Zheng, Yu Song, Richard Dawes, Daiqian Xie, Jingsong Zhang, Hua Guo
Summary: The dissociation dynamics of the nonadiabatic predissociation system HCO is strongly modulated by parent rotational quantum numbers, leading to a unique purely quantum mechanical behavior. The appearance of vibrational ground and excited states of CO product is attributed to the dependence of vibronic resonance lifetime on parent rotational angular momentum quantum numbers coupled with transient intensity borrowing.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Astronomy & Astrophysics
Christian Balanca, Ernesto Quintas-Sanchez, Richard Dawes, Fabien Dumouchel, Francois Lique, Nicole Feautrier
Summary: In this study, state-to-state rate coefficients of C4H- in collision with both ortho- and para-H-2 were determined, with a newly computed 4D potential energy surface. The differences between the ortho- and para-H-2 rate coefficients were found to be small, indicating similar behavior in collision with C4H-.
MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY
(2021)
Article
Astronomy & Astrophysics
Karlis Dzenis, Alexandre Faure, B. A. McGuire, A. J. Remijan, P. J. Dagdigian, C. Rist, R. Dawes, E. Quintas-Sanchez, F. Lique, M. Hochlaf
Summary: The theoretical rotational cross sections for propylene oxide colliding with cold He atoms were obtained using a high-accuracy potential energy surface. The results were combined with radiative data and analyzed using a non-LTE radiative transfer model, revealing the cold gas characteristics of propylene oxide in the Sgr B2(N) molecular cloud.
ASTROPHYSICAL JOURNAL
(2022)
Article
Chemistry, Physical
Maciej Gancewski, Hubert Jozwiak, Ernesto Quintas-Sanchez, Richard Dawes, Franck Thibault, Piotr Wcislo
Summary: This study presents a highly accurate potential energy surface for the collision between O-2 and N-2 molecules, and uses it for quantum scattering calculations, modeling the shape of O-2 fine structure line perturbed by N-2 collisions at 118 GHz. The calculated collisional broadening of the line is in good agreement with experimental data over a wide temperature range relevant for the terrestrial atmosphere, indicating a step towards populating spectroscopic databases with ab initio line shape parameters for atmospherically relevant systems.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Ernesto Quintas-Sanchez, Richard Dawes, Otoniel Denis-Alpizar
Summary: An accurate ground-state intermolecular potential energy surface was calculated for the HCS+-H-2 complex using ab initio methods. The surface was used to compute rovibrational energies, rotational constants, and close-coupling quantum scattering calculations at low collision energies. The study also discussed trends and propensities of rotational inelastic state-to-state cross sections of HCS+ by collision with para- and ortho-H-2.
Article
Optics
Eric S. Endres, Steve Ndengue, Olga Lakhmanskaya, Seunghyun Lee, Francesco A. Gianturco, Richard Dawes, Roland Wester
Summary: The study found that collision rates between OH- J = 0 <-> 1 and helium at different collision energies show a temperature-dependent trend, with the experimental and calculated results showing good agreement.
Article
Chemistry, Physical
Cheikh T. Bop, Ernesto Quintas-Sanchez, Sangeeta Sur, Mathurin Robin, Francois Lique, Richard Dawes
Summary: This study examines the role of oxygen molecules and argon atoms in collision processes, investigating how their interaction impacts atmospheric chemistry and dynamics. The findings highlight the importance of collision frequency, energy transfer efficiency, and species concentrations in diverse environments.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)