Article
Chemistry, Physical
Zahra Jamshidi, Sahar Ashtari-Jafari, Aleksei Smirnov, Elena Solovyeva
Summary: Experimental and theoretical investigations on the surface-enhanced resonant Raman spectroscopy (SERRS) of 4,4'-diaminotolane absorbed on silver reveal unique features compared to normal Raman and SERS on gold. The dependence of SERS spectra on excitation lines has been studied, and theoretical calculations based on the Herzberg-Teller correction show good agreement with experimental results, highlighting the importance of charge-transfer transitions in enhancing both totally and non-totally symmetric modes.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Multidisciplinary Sciences
Jon G. C. Kragskow, Jonathan Marbey, Christian D. Buch, Joscha Nehrkorn, Mykhaylo Ozerov, Stergios Piligkos, Stephen Hill, Nicholas F. Chilton
Summary: The coupling between vibrations and electronic spins, known as vibronic coupling, has a significant impact on the spin state lifetime in molecular magnets and qubits. This study presents direct measurements of vibronic transitions in a molecular magnet, highlighting the critical role of an envelope effect in the spectra. The research shows that vibronic coupling is strongest for vibrational modes that distort the first coordination sphere and break the C-3 symmetry of the molecule, providing new insights towards controlling vibronic coupling in molecules.
NATURE COMMUNICATIONS
(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, Physical
Robert B. Weakly, James D. Gaynor, Munira Khalil
Summary: This paper demonstrates experimental techniques for mapping coupled electronic and vibrational coordinates in complex systems through polarization-selective 2D VE and 2D EV spectroscopies. The study emphasizes the relationships between vibronic coupling parameters, Hamiltonian terms, and non-Condon effects, showing how they impact spectroscopic observables. The simulations of polarization-selective 2D EV and 2D VE spectra provide insights into measuring parameters of the vibronic Hamiltonian and non-Condon effects.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Keith Gilmore
Summary: This study summarizes the theoretical progress and potential predictive first-principles calculations of electron-phonon interactions in the case of dispersive phonons using resonant inelastic X-ray scattering (RIXS). The relation between coupling constant measured by RIXS and the standard electron-phonon coupling probed by transport measurements is discussed. Example calculations for crystalline MgO are provided.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Laura D. Elmendorf, Thomas C. Brunold
Summary: Understanding the reactivities of cobalamins requires knowledge of their geometric and electronic structures. In this study, the ORCA_ASA computational tool was used with B3LYP and BP86 functionals to predict Abs bandshapes and rR spectra for vitamin B-12. The ORCA_ASA/B3LYP-computed Abs envelope and rR spectra were in good agreement with experimental data, while BP86 failed to reproduce them. This finding is important for understanding the different modeling of electronic properties by these density functionals.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Thomas J. Penfold, Julien Eng
Summary: Excited state dynamics are important across various scientific fields, usually requiring an accurate description of the coupled electronic-nuclear motion. The challenge lies in calculating the potential energy surface (PES) for nuclear evolution. This paper introduces a metric called the global anharmonicity parameter (GAP) to assess the accuracy of a linear vibronic coupling (LVC) potential and applies it to three molecules with different rigidity in their excited states.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Arun Kumar Kanakati, S. Mahapatra
Summary: This study investigates the nuclear dynamics in the first six vibronically coupled electronic states of pentafluorobenzene radical cation using vibronic coupling theory and quantum dynamical methods. A 6 x 6 vibronic Hamiltonian is constructed based on symmetry selection rules and electronic Hamiltonian elements expansion. Extensive quantum chemistry calculations are conducted to establish adiabatic electronic energies and their coupling surfaces, with both time-independent and time-dependent quantum mechanical methods used for nuclear dynamics calculations. The vibronic spectrum of electronic states is calculated and compared with experimental results, while the impact of increasing fluorination on radiative emission is also examined.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Jianye Huang, Bocheng Ding, Yunfei Feng, Ruichang Wu, Lifang Tian, Xiao-Jing Liu
Summary: Vibronic coupling, a critical mechanism in chemical reactions, is challenging to quantitatively evaluate and experimentally prove. In this study, we separated resonant Auger decay channels leading to the lowest dissociation limit in N-2 molecules by exciting a vibrational level of the intermediate N 1s -> pi*(g) core-excited state. By analyzing three kinetic energy release spectra at different vibrational quantum numbers, we provide the first experimental proof of vibronic coupling between two resonant Auger final states, 1(2) Pi(g) and 2 (2) Pi(g).
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Rudraditya Sarkar, Marie-Catherine Heitz, Martial Boggio-Pasqua
Summary: This study provides a detailed insight into the structure of absorption bands of the photochromic couple DHP/CPD using vibronic coupling theory. Two separate model molecular Hamiltonians are constructed based on DFT and time-dependent DFT calculations, allowing for a thorough analysis of potential energy curves and stationary points on multi-dimensional potential energy surfaces. Quantum nuclear dynamics studies on the electronic excited states of DHP and CPD reveal the impact of non-adiabatic effects on the formation of vibronic structures of absorption bands.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Alberto Martinelli, Emanuela Sartori, Marta Campolucci, Maurizio Ferretti, Zeger Hens, Federico Locardi
Summary: Alkaline earth copper silicate-based pigments exhibit interesting near-infrared photoemission, with slightly different optical properties influenced by local structure variations. X-ray powder diffraction and pair distribution function analysis revealed a complex structural dynamic involving the tetrahedral framework embedding the copper chromophore group. This structure dynamic induces vibronic coupling and affects absorption and emission spectra in the visible and near-infrared range.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
A. B. Trofimov, A. D. Skitnevskaya, E. K. Grigoricheva, E. Gromov, H. Koppel
Summary: In this study, theoretical investigations were conducted to study the vibronic interactions and associated nuclear dynamics in the ground and two excited states of the imidazole radical cation. The results were used to interpret recent experimental measurements. High-level electronic structure calculations revealed the close energy proximity and non-adiabatic effects between the A (2)A' and B (2)A states, confirming the existence of pronounced vibronic coupling. The modeling approach utilized the three-state linear vibronic coupling problem and ab initio calculations for parameter derivation, and the calculated ionization spectrum showed good agreement with experimental data.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Viktoriia Savchenko, Victor Ekholm, Iulia Emilia Brumboiu, Patrick Norman, Annette Pietzsch, Alexander Foehlisch, Jan-Erik Rubensson, Johan Grasjoe, Olle Bjorneholm, Conny Sathe, Minjie Dong, Thorsten Schmitt, Daniel McNally, Xingye Lu, Pavel Krasnov, Sergey P. Polyutov, Faris Gel'mukhanov, Michael Odelius, Victor Kimberg
Summary: This study presents a theoretical and experimental investigation of gas phase and liquid acetic acid using resonant inelastic x-ray scattering (RIXS) spectroscopy, comparing different levels of theory and revealing nuclear dynamic effects in the oxygen K-edge absorption excitation energy scan. Experimental data show that the theoretical model based on a dimer describes well the hydrogen bond formation in the liquid phase.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Daniel Aranda, Fabrizio Santoro
Summary: Hexahelicene, as a prototype of an extended pi-conjugated system with axial chirality, challenges computational methods due to its complex spectra. By utilizing time-dependent density functional theory and multiconfigurational time-dependent Hartree methods, the nonadiabatic ABS and ECD vibronic spectra of hexahelicene have been successfully computed. The proposed approach is a general tool for studying the photophysical properties of pi-conjugated systems with a dense manifold of interacting electronic states.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Multidisciplinary Sciences
Yuanheng Wang, Jiajun Ren, Zhigang Shuai
Summary: The widely known Energy Gap Law (EGL) predicts an exponential increase in the non-radiative decay rate as the energy gap narrows, which hinders the development of near-infrared emissive molecular materials. However, recent experiments suggest that exciton delocalization in molecular aggregates can counteract EGL and facilitate near-infrared emission. In this work, the authors develop a nearly exact method to evaluate the non-radiative decay rate for exciton-phonon coupled molecular aggregates and reveal the underlying physical picture.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Stephanie N. Choing, Aaron J. Francis, Graham Clendenning, Michael S. Schuurman, Roger D. Sommer, Isaac Tamblyn, Walter W. Weare, Tanja Cuk
JOURNAL OF PHYSICAL CHEMISTRY C
(2015)
Article
Chemistry, Physical
Simon P. Neville, Vitali Averbukh, Serguei Patchkovskii, Marco Ruberti, Renjie Yun, Majed Chergui, Albert Stolow, Michael S. Schuurman
FARADAY DISCUSSIONS
(2016)
Article
Chemistry, Physical
Ryan J. MacDonell, Oliver Schalk, Ting Geng, Richard D. Thomas, Raimund Feifel, Tony Hansson, Michael S. Schuurman
JOURNAL OF CHEMICAL PHYSICS
(2016)
Article
Chemistry, Physical
Simon P. Neville, Vitali Averbukh, Marco Ruberti, Renjie Yun, Serguei Patchkovskii, Majed Chergui, Albert Stolow, Michael S. Schuurman
JOURNAL OF CHEMICAL PHYSICS
(2016)
Article
Chemistry, Physical
Simon P. Neville, Yanmei Wang, Andrey E. Boguslavskiy, Albert Stolow, Michael S. Schuurman
JOURNAL OF CHEMICAL PHYSICS
(2016)
Article
Chemistry, Physical
Simon P. Neville, Vitali Averbukh, Serguei Patchkovskii, Marco Ruberti, Renjie Yun, Majed Chergui, Albert Stolow, Michael S. Schuurman
FARADAY DISCUSSIONS
(2016)
Article
Physics, Multidisciplinary
Xiaoyan Ding, M. Haertelt, S. Schlauderer, M. S. Schuurman, A. Yu. Naumov, D. M. Villeneuve, A. R. W. McKellar, P. B. Corkum, A. Staudte
PHYSICAL REVIEW LETTERS
(2017)
Article
Chemistry, Physical
Serguei Patchkovskii, Michael S. Schuurman
JOURNAL OF PHYSICAL CHEMISTRY A
(2014)
Article
Chemistry, Physical
Oliver Schalk, Michael S. Schuurman, Guorong Wu, Peter Lang, Melanie Mucke, Raimund Feifel, Albert Stolow
JOURNAL OF PHYSICAL CHEMISTRY A
(2014)
Article
Physics, Multidisciplinary
Kwanghsi Wang, Vincent McKoy, Paul Hockett, Michael S. Schuurman
PHYSICAL REVIEW LETTERS
(2014)
Article
Multidisciplinary Sciences
Heide Ibrahim, Benji Wales, Samuel Beaulieu, Bruno E. Schmidt, Nicolas Thire, Emmanuel P. Fowe, Eric Bisson, Christoph T. Hebeisen, Vincent Wanie, Mathieu Giguere, Jean-Claude Kieffer, Michael Spanner, Andre D. Bandrauk, Joseph Sanderson, Michael S. Schuurman, Francois Legare
NATURE COMMUNICATIONS
(2014)
Proceedings Paper
Computer Science, Interdisciplinary Applications
H. Ibrahim, S. Beaulieu, V. Wanie, T. Endo, B. Wales, X. -M. Tong, M. S. Schuurman, J. Sanderson, F. Legare
PROCEEDINGS OF THE INTERNATIONAL CONFERENCE OF COMPUTATIONAL METHODS IN SCIENCES AND ENGINEERING 2017 (ICCMSE-2017)
(2017)
Article
Optics
Serguei Patchkovskii, Michael S. Schuurman
Article
Chemistry, Physical
Kwanghsi Wang, Vincent McKoy, Paul Hockett, Albert Stolow, Michael S. Schuurman
CHEMICAL PHYSICS LETTERS
(2017)
Proceedings Paper
Engineering, Electrical & Electronic
Heide Ibrahim, Benji Wales, Samuel Beaulieu, Bruno E. Schmidt, Nicolas Thire, Eric Bisson, Christoph T. Hebeisen, Vincent Wanie, Mathieu Giguere, Jean-Claude Kieffer, Michael Spanner, Andre D. Bandrauk, Michael S. Schuurman, Joseph Sanderson, Francois Legare
XXIX INTERNATIONAL CONFERENCE ON PHOTONIC, ELECTRONIC, AND ATOMIC COLLISIONS (ICPEAC2015), PTS 1-12
(2015)