Article
Chemistry, Physical
P. Bryan Changala, Nadav Genossar, Joshua H. Baraban
Summary: This article presents a derivation method for the harmonic vibrational auto-correlation function that is applicable to both real and imaginary harmonic frequencies. By utilizing Lie algebra techniques, complex exponential operator calculations are transformed into simpler matrix formulas. The study is significant for correcting the harmonic Franck-Condon approximation and performing quantitative simulations of molecular electronic spectra.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Zhiwen Luan, Yanlin Fu, Yuxin Tan, Yaling Wang, Baokun Shan, Jie Li, Xiaoguo Zhou, Wentao Chen, Lijie Liu, Bina Fu, Dong H. Zhang, Xueming Yang, Xingan Wang
Summary: A comprehensive understanding of dissociation mechanisms is crucial in small molecule photochemistry. This study investigates the photodissociation dynamics of H2S+ near 337 nm and reveals significant changes in product distributions within a small excitation energy range. The analysis based on full-dimensional potential energy surfaces identifies nonadiabatic pathways as responsible for the observed variation in product distributions. This study provides in-depth insight into nonadiabatic dynamics in photochemistry.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
I. B. Bersuker
Summary: In this paper, we discuss the different versions of the Jahn-Teller effect (JTE) and their adiabatic potential energy surfaces (APES) as indicators of spontaneous symmetry breaking (SSB) in atomic matter. We emphasize the importance of solving the Schrodinger equation with the APES to observe the effects of JTE, such as tunneling splitting and reduction of spin-orbit coupling. Using the example of electric field polarization in the BaTiO3 crystal, we demonstrate the methodology and present a novel effect: orientational polarization of solids.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Joanna Jankowska, Robert W. Gora
Summary: This study predicts a strong photostability of the 8-oxo-hypoxanthine system through quantum chemistry calculations, attributing this effect to ultrafast nonradiative relaxation caused by puckering of the 6-membered heterocyclic ring.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Yue-Rou Zhang, Dao-Fu Yuan, Lai-Sheng Wang
Summary: Although the adiabatic potential energy surfaces are crucial in understanding the electronic structure and spectroscopy of molecular systems, nonadiabatic effects due to electronic states coupling by nuclear motions are common in complex molecular systems. In this study, the complex vibronic levels of the triazolyl radical were completely unraveled using photodetachment spectroscopy and resonant photoelectron imaging. The experimental vibronic information obtained will be valuable in validating theoretical models for treating nonadiabatic effects involving multiple electronic states.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Mengqi Wang, Yanan Shi, Yurong Guo, Yibing Chen, Chenyang Zhao, Yi Zhou, Yongze Xiao, Ye Wang, Song Zhang, Bing Jin, Zibo Wu, Guangjiu Zhao
Summary: This study proposes natural molecules chlorogenic acid (CA) and isochlorogenic acid A (ICAA) as potential sunscreens for the first time, revealing their non-radiative energy relaxation mechanisms and photoisomerization channels. The dual conjugated system improves energy absorption efficiency, providing insights for designing novel sunscreen compounds.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
Simon P. Neville, Michael S. Schuurman
Summary: A perturbative approximation, termed DFT/MRCI(2), has been introduced for the combination of density functional theory and multireference configuration interaction (DFT/MRCI) approach. This method, utilizing QDPT and Epstein-Nesbet partitioning, significantly reduces computational cost while maintaining excellent accuracy.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
Xu Sang, Qingru Wang, Xiaoli Gao, Adnan Khan, Ziyu Chen, Jiaxin Yang, Ming Feng, Lisa Liu, Feng Song, Wei Huang
Summary: Based on the interaction between Eu(iii) complexes and liquid crystals (LCs), three general approaches to obtain a tunable emitting color for RE/LC composites are presented.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Physical
Yasuki Arasaki, Kazuo Takatsuka
Summary: The dynamics and energy structure of highly fluctuating nonadiabatic electron wavepackets are studied using Energy Natural Orbitals (ENOs). These wavepackets are sampled from the highly excited states of clusters of 12 boron atoms. The ENO representation provides an invariant energy orbital picture for both static and time-dependent electronic wavefunctions. The study reveals the mechanism of the coexistence of large electronic fluctuation and strong chemical bonds within the molecule.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Donghui Li, Jianwei Cao, Haitao Ma, Wensheng Bian
Summary: This study investigates the low-lying electronic states and feasibility of direct laser cooling of AsH, SbH, and BiH, taking into account the spin-orbit coupling effects. The results show significant intersystem crossings and spin-orbit couplings, which impact the laser cooling process. The difficulty of cooling heavier hydrides increases with enhanced spin-orbit coupling effects as the crossing point location shifts down towards the ground vibrational level.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
David Chicharro, Alexandre Zanchet, Aymen Bouallagui, Luis Rubio-Lago, Alberto Garcia-Vela, Luis Banares, Sonia Marggi Poullain
Summary: A site-specific hydrogen-atom elimination reaction has been found to occur in various alkyl radicals during photodissociation, depending on the internal energy content prior to dissociation and involvement of vibrational promoting modes. The methyl deformation mode and CH bending motion promote this fast hydrogen-atom elimination channel in alkyl radicals.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Francois O. Laforge, Juneseo Lee, Herschel A. Rabitz
Summary: Physicists revolutionized the scientific world with the invention of the laser in 1960. In the following two decades, fruitful collaboration between theoreticians and experimentalists led to progress in laser-selective chemistry. This Perspective argues that the roots of quantum control can be traced back to efforts to manipulate chemical reactions with lasers, reaching as far back as the invention of the laser in 1960.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Frederik Thorning, Frank Jensen, Peter R. Ogilby
Summary: Research on the interactions between molecular oxygen and perturbing species has been ongoing for at least 70 years, focusing on the perturbation of electronic states and transitions. The study shows that the atoms in a perturbing species closest to oxygen play a significant role in spin-orbit interactions, simplifying the complexity of large systems. The spin-orbit coupling matrix element can be estimated from the induced energy splitting of oxygen's orbitals, which may provide further insights into the O-2(a(1)Delta(g)) -> O-2(X-3 Sigma(-)(g)) transition.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Georgia Christopoulou, Thierry Tran, Graham A. Worth
Summary: In this study, the DD-vMCG method was used to investigate the multidimensional photodissociation dynamics of phenol, including calculations involving six electronic states and a comparison to a 4-state model. The inclusion of the fifth singlet excited state was shown to significantly impact the nonadiabatic photodissociation process. Further insights into the decay mechanism were provided through state population and flux analysis from the DD-vMCG simulations.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Seonghoon Choi, Jiri Vanicek
Summary: The study introduces a method to assess the potential errors introduced by neglecting residual couplings by comparing quantum dynamics simulations with or without these couplings. The results show that neglecting residual couplings can lead to inaccurate dynamics, while simulations with the exact quasidiabatic Hamiltonian always yield accurate results.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Thomas Quenzel, Daniel Timmer, Moritz Gittinger, Jennifer Zablocki, Fulu Zheng, Manuela Schiek, Arne Lutzen, Thomas Frauenheim, Sergei Tretiak, Martin Silies, Jin-Hui Zhong, Antonietta De Sio, Christoph Lienau
Summary: Increasing the exciton coherence length of squaraine aggregates by preparing them on a metallic substrate rather than a dielectric substrate can improve the transport properties and optical response of molecular nanostructures. The reduced disorder and enhanced exciton-plasmon coupling effects observed on a gold film demonstrate the potential for improving coherent transport properties of molecular aggregates and tailoring their collective optical response for quantum optical applications.
Article
Chemistry, Physical
Hassiel Negrin-Yuvero, Aliya Mukazhanova, Victor M. Freixas, Sergei Tretiak, Sahar Sharifzadeh, Sebastian Fernandez-Alberti
Summary: Perylene diimide (PDI) is a promising material for organic optoelectronic devices, and its properties have been analyzed in detail using nonadiabatic excited-state molecular dynamics simulations. The study found that the vibronic relaxation of PDI's photoexcitation involves persistent modulations in the spatial localization of electronic and vibrational excitations, driven by strong vibronic couplings. This behavior is independent of the molecule's symmetry, suggesting potential applications in tunable functionalities.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Aaron Forde, Dibyajyoti Ghosh, Dmitri Kilin, Amanda C. Evans, Sergei Tretiak, Amanda J. Neukirch
Summary: Inducing chiroptical activity in semiconductors by deploying chiral organic molecules as capping ligands for nanocrystals shows emergent chiroptical signatures. Chirality transfer in CsPbX3 clusters capped with chiral diaminocyclohexane enantiomers is best explained by chiral molecular dipole-cluster transition dipole coupling. Increased anisotropy factors proportional to surface ligand density provide insight for improving chiroptical functionality in semiconductor nanomaterials.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Ashutosh Kumar, Ayush Asthana, Conner Masteran, Edward F. Vleev, Yu Zhang, Lukasz Cincio, Sergei Tretiak, Pavel A. Dub
Summary: This paper attempts to reduce the quantum resource requirements for molecular simulations on quantum computers while maintaining the desired accuracy. By using compact and balanced transcorrelated Hamiltonians to describe both the ground and excited states of molecular systems, and employing the VQE method and qEOM formalism, the number of required quantum gates and the deviations in excitation energies can be greatly reduced.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Dustin A. Tracy, Sebastian Fernandez-Alberti, Sergei Tretiak, Adrian E. Roitberg
Summary: We present a method for linking the NEXMD package to the SANDER package to perform excited-state adiabatic QM/MM simulations. The method has been tested using a substituted polyphenylene vinylene oligomer in vacuum and explicit solvents, and compared with implicit solvent implementations. The impact of the QM region expansion has also been analyzed.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Victor Manuel Freixas, Sergei Tretiak, Sebastian Fernandez-Alberti
Summary: Progress in organic synthesis allows the exploration of diverse molecules with new structural topologies. The recently synthesized infinitene is a helically twisted figure-eight molecule with unique optoelectronic properties suitable for applications in nanoelectronics and photonics. However, the photophysical properties of infinitene have not been investigated.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Aaron Forde, Victor M. Freixas, Sebastian Fernandez-Alberti, Amanda J. Neukirch, Sergei Tretiak
Summary: This study characterizes the energetic alignment of excitonic and charge-transfer states in a BODIPY-TPA molecular complex using time-dependent density functional theory. The rationalization of charge-transfer state emission provides a foundation for exploring charge-transfer using ab initio excited-state nonadiabatic dynamics.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Hsinhan Tsai, Dibyajyoti Ghosh, Eli Kinigstein, Bogdan Dryzhakov, Honora Driscoll, Magdalena Owczarek, Bin Hu, Xiaoyi Zhang, Sergei Tretiak, Wanyi Nie
Summary: The dynamic structure changes in metal halide perovskite lattice upon photoexcitation and its impact on carrier transport properties in Ruddlesden-Popper phase perovskite thin films are reported in this study. Time-resolved X-ray scattering technique reveals rapid lattice expansion and slow relaxation over 100 ns after photoexcitation. The expansion is attributed to lattice thermal fluctuations caused by photon energy deposition. High laser powers induce strong local structural disorder, increasing the charge dissociation activation energy and leading to localized transport.
Article
Mechanics
M. Serrano, K. Larkin, M. Ghommem, S. Tretiak, A. Abdelkefi
Summary: A multi-purpose energy harvesting microgyroscope system based on piezoelectric materials is proposed for small devices in remote areas. Numerical analysis shows that a system with a non-symmetric beam design is suitable for broadband energy harvesting. The nonlinear softening effects create a broadband frequency response with high voltage output, but careful selection of DC and AC voltages is necessary to avoid dynamic pull-in.
EUROPEAN JOURNAL OF MECHANICS A-SOLIDS
(2023)
Article
Mechanics
M. Serrano, K. Larkin, S. Tretiak, A. Abdelkefi
Summary: Most microelectromechanical systems (MEMS) are made from brittle materials that are prone to cracking. Understanding the potential influences cracks in MEMS is necessary for the longevity of these systems. This study developed an electromechanical model to capture the impacts of cracks on the performance of a damaged energy harvesting microgyroscope, and numerical methods were used to approximate the damage associated with distributed crack networks. The study revealed that cracks can significantly affect the static and dynamic behaviors of the microgyroscope energy harvester.
EUROPEAN JOURNAL OF MECHANICS A-SOLIDS
(2023)
Article
Chemistry, Physical
Hassiel Negrin-Yuvero, Victor M. Freixas, Dianelys Ondarse-Alvarez, Ana E. Ledesma, Sergei Tretiak, Sebastian Fernandez-Alberti
Summary: The photoexcitation, energy relaxation, and redistribution of a recently synthesized zigzag carbon nanobelt were studied using molecular dynamics simulations. The transition dipole moments and electronic transition density were found to gradually change during the internal conversion process. The electronic relaxation involved long-lived states with large energy gaps and changes in symmetry. These results provide insights into the excited-state properties of the zigzag nanobelt and can inspire the design of tailored nanobelts for specific nanoelectronic and photonic applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Chintam Hanmandlu, Rohan Paste, Hsinhan Tsai, Shyam Narayan Singh Yadav, Kuan-Wen Lai, Yen-Yu Wang, Chandra Shekar Gantepogu, Chen-Hung Hou, Jing-Jong Shyue, Yu-Jung Lu, Tushar Sanjay Jadhav, Jian-Ming Liao, Hsien-Hsin Chou, Hui Qi Wong, Chao-Sung Lai, Dibyajyoti Ghosh, Sergei Tretiak, Ta-Jen Yen, Hung-Ju Yen, Chih-Wei Chu
Summary: This study used a holistic interface strategy to enhance the efficiency and stability of perovskite solar cells by decreasing the number of interfacial defect states. The researchers utilized three-dimensional triphenylamine-based nanographene precursors to form a bridge between the perovskite film and the hole transport layer, resulting in improved performance characteristics.
Article
Chemistry, Physical
Hassiel Negrin-Yuvero, Victor M. Freixas, Dianelys Ondarse-Alvarez, Ana E. Ledesma, Sergei Tretiak, Sebastian Fernandez-Alberti
Summary: Progress in the synthesis of new carbon nanorings and nanobelts broadens the library of materials with unique structural and optical properties that can be attractive for further potential applications in host-guest chemistry, nanoelectronics, and photonics. In this study, we investigate the photoexcitation and subsequent energy relaxation and redistribution of a recently synthesized zigzag carbon nanobelt using nonadiabatic excited state molecular dynamics simulations. Our results reveal the excited-state dynamical properties of the zigzag-type nanobelt that differentiate this molecule from other nanobelts, providing insights for further designs tailored for specific nanoelectronic and photonic applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Dibyajyoti Ghosh, Carlos Mora Perez, Oleg Prezhdo, Wanyi Nie, Sergei Tretiak, Amanda J. Neukirch
Summary: Mixed A-cation halide perovskites have shown great potential for next-generation optoelectronic applications due to their attractive charge carrier transport properties and enhanced stability. In this study, we investigate the influence of A-cation mixing on the relaxation processes of hot charge carriers in FA(1-x)Cs(x)PbI(3) materials using nonadiabatic molecular dynamics and time-domain density functional theory methods. Our results demonstrate that the partial substitution of organic FA species with inorganic Cs cations significantly extends the relaxation times of hot electrons and hot holes. The understanding of the relationship between the dynamic structure and carrier relaxation allows us to propose rational design principles for enhancing the hot carrier lifetimes in photoactive materials.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Victor M. Freixas, Daniel Keefer, Sergei Tretiak, Sebastian Fernandez-Alberti, Shaul Mukamel
Summary: This study explores the photoinduced ultrafast coherent inter-chromophore energy redistribution in a triarylamine trimer using nonadiabatic excited state molecular dynamics followed by simulations of X-ray Raman signals. The research reveals the presence of multiple non-deterministic photoinduced pathways during the ultrafast inter-branch migration of the excitation, resulting in spatial exciton scrambling and loss of phase information at long times. The study demonstrates that X-ray Raman spectroscopy is a valuable tool for detecting ultrafast molecular coherences or their absence.