Article
Chemistry, Applied
Qian Zhou, Huitian Du, Zhen Chen, Yuan Yu, Junfeng Ren, Shenghao Han, Jihui Fan, Zhiyong Pang
Summary: This study successfully prepared cocrystals of acridine and 1,2,4,5-tetracyano-benzene by self-assembly, showing novel luminescent properties. The findings may have important implications for the design and applications of nonlinear optical materials.
Article
Chemistry, Physical
Zoltan Szakacs, Eric Vauthey
Summary: Excited-state symmetry breaking (ES-SB) is common in multibranched electron donor-acceptor (DA) molecules in polar environments. However, due to the lack of an unambiguous spectroscopic signature in the UV-vis region, electronic transient absorption (TA) has not been the preferred method for real-time observation of this phenomenon.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Isabel M. Klein, Hanzhe Liu, Danika Nimlos, Alex Krotz, Scott Kevin Cushing
Summary: This article introduces a novel ab initio Bethe-Salpeter equation method for studying photoexcited-state effects in various material systems. The method demonstrates precise calculations of XUV absorption spectra and provides physical intuition on the origin of transient XUV spectra.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Physics, Applied
Sayan Prodhan, Kamlesh Kumar Chauhan, Tara Singha, Manobina Karmakar, Nikhilesh Maity, Renjith Nadarajan, Partha Kumbhakar, Chandra Sekhar Tiwary, Abhishek Kumar Singh, Manikoth M. Shaijumon, Prasanta Kumar Datta
Summary: Semiconductors based on group-VI 2D materials, such as bilayer selenium (Se), show potential for optoelectronic applications. This study investigates the carrier dynamics of bilayer 2D Se in one-photon and multi-photon absorption regimes. The results show that the carrier lifetime can be used to predict the photo-responsivity of 2D Se photo-detectors operating in the one-photon-absorption regime. Additionally, bilayer 2D Se exhibits a significant two-photon absorption cross section and can function as a sub-bandgap photo-detector. The study also reveals the dominant carrier recombination process in different absorption regimes, and suggests the possibility of using 2D Se as a saturable absorber material for passive Q-switching.
APPLIED PHYSICS LETTERS
(2023)
Article
Chemistry, Physical
Nan Zhang, Lu Liu, Haixia Chang, Ke Liu, Taihong Liu, Liping Ding, Yu Fang
Summary: Versatile coupling theories have been developed to explain the unusual aggregation phenomena of multipolar chromophores. This study investigates the diverse excitonic couplings and tunability of a quadrupolar squaraine dye protonated by trifluoroacetic acid in different solvation media. Subtle changes in the solvent and ion pair lead to significant variations in the aggregation and optical properties of the donor-acceptor-donor (D-A-D)-type SQC6.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
KatelynM. Duncan, Hannah M. Byers, Madaline E. Houdek, Simon K. Roy, Austin Biaggne, Matthew S. Barclay, Lance K. Patten, Jonathan S. Huff, Donald L. Kellis, Christopher K. Wilson, Jeunghoon Lee, Paul H. Davis, Olga A. Mass, Lan Li, Daniel B. Turner, John A. Hall, William B. Knowlton, Bernard Yurke, Ryan D. Pensack
Summary: In this study, the electronic structure and excited-state dynamics of monomers and aggregates of four asymmetric polymethine dyes templated via DNA were characterized. The asymmetric polymethine dye monomers exhibited large transition dipole moments (mu), appreciable static dipole moment differences (Delta d), and long excited-state lifetimes (tau(p)). Dye Dy 754 displayed the strongest propensity for aggregation and exciton delocalization, with promising values of the excitonic hopping parameter (J).
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Multidisciplinary Sciences
Sitakanta Satapathy, Mandeep Khatoniar, Divya K. Parappuram, Bin Liu, George John, Johannes Feist, Francisco J. Garcia-Vidal, Vinod M. Menon
Summary: The formation of organic exciton-polaritons can selectively tune the isomer emission of organic molecules, allowing for efficient funneling of excitation between molecular isomers. This new relaxation pathway helps recognize pure emission from isomeric states that do not contribute to emission under normal conditions.
Article
Multidisciplinary Sciences
Andrea B. Grafton, Adam D. Dunkelberger, Blake S. Simpkins, Johan F. Triana, Federico J. Hernandez, Felipe Herrera, Jeffrey C. Owrutsky
Summary: The study observed the spectroscopic signatures and relaxation dynamics of vibration-polaritons formed from the NO band of nitroprusside, using a quantum model to explain the results. The decay of polariton features was found to be slower, indicating their partial incoherent population characteristics.
NATURE COMMUNICATIONS
(2021)
Article
Materials Science, Multidisciplinary
Xiao-Qing Yan, Xin Zhao, Haijie Xu, Lei Zhang, Dongqi Liu, Yuchen Zhang, Changfu Huo, Fang Liu, Junfang Xie, Xiao Dong, Zhi-Bo Liu, Jian-Guo Tian
Summary: CIPS is a ferroelectric material with a low phase transition temperature, allowing for convenient modulation of its optical properties through temperature control. As temperature increases, PL emission intensity and excitation efficiency decrease significantly, while two-photon absorption coefficient increases, with carrier relaxation times remaining unchanged.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Physical
Yanmei Wang, Zhenfei Gu, Xulan Deng, Bing Zhang
Summary: Through real-time tracking of the UV-light-triggered isomerization of propanal in the 3s Rydberg state, it was found that the conversion barrier is approximately 1500 +/- 100 cm(-1), and the photoisomerization yield and conversion rate depend strongly on the excitation energy.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Ziying Tang, Huying Zheng, Yaqi Wang, Runchen Wang, Zhiren Qiu, Yan Shen, Jie Zhou, Shichen Su, Lin Li, Hai Zhu
Summary: This study demonstrates the realization of ultralow-threshold six-photon-excited upconversion lasing through cavity quantum electrodynamics effects in a plasmonic microcavity. The Purcell factor in hybrid whisper-gallery mode is significantly enhanced, leading to enhanced nonlinear light-matter interactions. In addition, the temperature and polarization characteristics of upconversion lasing via a plasmonic-WGM approach show distinct evolution compared to a bare microwire.
Article
Chemistry, Physical
Stanislav L. Bondarev, Tamara F. Raichenok, Sergei A. Tikhomirov, Nikolai G. Kozlov, Tatyana Mikhailova, Anatoly I. Ivanov
Summary: A synthesized acridine-dione derivative with a quadrupolar motif was studied for its spectral properties in different solvent conditions, revealing that symmetry breaking is mainly due to the formation of asymmetric strong hydrogen bonds on one side of the molecule. In specific mixtures of solvents, it was found that a certain threshold concentration of methanol is necessary for symmetry breaking to occur, with concentrations below this threshold not leading to fluorescence quenching.
JOURNAL OF PHYSICAL CHEMISTRY B
(2021)
Article
Chemistry, Medicinal
Xue-Li Hao, Ai-Min Ren, Liang Zhou
Summary: Hydrogen sulfide (H2S) has important physiological and pathological roles, but abnormal levels can cause diseases. Researchers have explored the mechanism of a turn-on probe for H2S monitoring and investigated the effect of geometric modifications on optical properties. They found that introducing electron-withdrawing substituent groups in benzopyran can suppress molecular skeleton vibration and improve two-photon absorption (TPA) ability, making it a potential material for biological imaging and H2S detection.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Chemistry, Organic
Huan Dai, Zhi-Bin Cai, Qiao-Xian Lou, Sheng-Li Li, Yu-Peng Tian
Summary: Four novel two-photon absorption compounds were synthesized conveniently and their optical properties, including large two-photon absorption cross-sections, were systematically investigated in various solvents. Compounds with dihexylamino donors exhibit good optical properties, which is supported by time-dependent density functional theory calculations.
Article
Chemistry, Multidisciplinary
Austen Moss, Youngwoo Jang, Jacob Arvidson, Vladimir N. Nesterov, Francis D'Souza, Hong Wang
Summary: A new synthetic method to fuse benzo[4,5]imidazo[2,1-a]isoindole to the porphyrin periphery has been developed, and its effects on aromaticity and electronic structures have been investigated. The fused benzoimidazo-isoindole component exhibits reactivity and the ability to bind with platinum(ii), resulting in the formation of novel homobimetallic and heterobimetallic porphyrin complexes. The fusion of benzoimidazo-isoindole on the porphyrin ring leads to bathochromically shifted absorptions and emissions, indicating extended conjugation of the porphyrin pi-system.
Article
Chemistry, Multidisciplinary
Felix Plasser, Anna Krylov, Andreas Dreuw
Summary: libwfa is an open-source software library for wavefunction analysis, offering a variety of analysis methods for post-processing excited-state calculations. These tools provide graphical representations of various excited-state processes and offer insights into electronic structure. The software is capable of automated processing of large data sets and establishes a link between many-body wavefunctions and physical and chemical models.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2022)
Article
Chemistry, Physical
Goran Giudetti, Igor Polyakov, Bella L. Grigorenko, Shirin Faraji, Alexander V. Nemukhin, Anna I. Krylov
Summary: This work explores the importance of transparency in reporting computational protocols for achieving reproducibility in QM/MM simulations. By simulating a chemical reaction in a biomolecule as a test case, the study shows that reproducing key energy calculations from two software packages is challenging. The results indicate that minor details of the QM/MM simulations need to be reported to ensure reproducibility, and suggestions are provided for developing practical guidelines for reporting biosimulation results.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Saikiran Kotaru, Sven Kahler, Maristella Alessio, Anna Krylov
Summary: The exchange coupling constants for a set of iron (III) binuclear and tetranuclear complexes are calculated using non-collinear spin-flip time-dependent density functional theory (NC-SF-TDDFT). The results show good agreement with experimentally derived values. The applicability of the Heisenberg model is explored by analyzing bonding patterns and natural orbitals (NO). The efficiency of the spin-flip protocol in computing exchange couplings and the utility of NO analysis in assessing the validity of effective spin Hamiltonians are demonstrated.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Pawel Wojcik, Eric R. Hudson, Anna Krylov
Summary: This study systematically investigates the diatomic radical-cations composed of a metal and a ligand, and finds that the electronic transitions in these cations for optical cycling are less effective compared to the successfully laser-cooled neutral molecules. Alternative transitions suitable for optical cycling are proposed, providing insights for the design of OCCs in charged or neutral molecules.
Article
Chemistry, Multidisciplinary
Manvendra Singh, Pawan Dhote, Daniel R. Johnson, Samuel Figueroa-Lazu, Christopher G. Elles, Zarko Boskovic
Summary: Photoexcitation of cyclic ketones leads to the expulsion of carbon monoxide and a mixture of products derived from diradical intermediates. The synthetic utility of this process is improved by using strained heterocyclic ketones. Photochemistry of 3-oxetanone and N-Boc-3-azetidinone, which proceed through Norrish type I cleavage of the C-C bond, has not been previously described. Ylides derived from these compounds undergo [3+2] cycloaddition with alkenes to produce substituted tetrahydrofurans and pyrrolidines, providing access to new chemical space.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Madhubani Mukherjee, T. P. Ragesh Kumar, Milos Rankovic, Pamir Nag, Juraj Fedor, Anna I. Krylov
Summary: We present a study that combines experimental and theoretical methods to investigate the interaction between electrons and molecules using pyrrole as a model system. The experimental two-dimensional electron energy loss spectra (EELS) provide information about the molecular vibrational states and electronic resonances. The calculations using complex-valued extensions of equation-of-motion coupled-cluster theory help identify the major EELS features. The results confirm previously described pi resonances and predict a low-lying resonance with a mixed character, providing insights into the vibrational excitation patterns observed in the EELS.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Kaushik D. D. Nanda, Sahil Gulania, Anna I. I. Krylov
Summary: The equation-of-motion coupled-cluster singles and doubles method with double electron attachment (EOM-DEA-CCSD) is extended to calculate two-photon absorption (2PA) cross sections of diradicals and polyenes. The performance of this new implementation is compared with the CC3 quadratic response theory approach. The EOM-DEA-CCSD 2PA cross sections are comparable to the CC3 results for twisted ethene, but show large discrepancies for hexatriene, explained by configurational analysis of the 2PA channels.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Kristen H. H. Burns, Timothy J. J. Quincy, Christopher G. G. Elles
Summary: This paper investigates the wavelength-dependent mechanism for sequential excitation of diarylethene molecular switches, revealing enhanced vibrational modes in different excitation spectra and providing insights into the ultrafast dynamics of higher-lying excited states following sequential two-photon excitation.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Saikiran Kotaru, Pavel Pokhilko, Anna I. Krylov
Summary: In this study, we propose a new method for computing spin-orbit couplings (SOCs) within a time-dependent density-functional theory (TD-DFT) framework. We use the Breit-Pauli Hamiltonian and Wigner-Eckart's theorem to calculate the SOC matrix elements. Benchmark calculations on organic molecules, diradicals, and a single-molecule magnet demonstrate the efficiency of our approach. Furthermore, the results indicate that the SOC is insensitive to the choice of functional or basis sets for organic molecules with states of the same characters, while it shows strong functional dependence for specific small diradical systems.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Nayanthara K. Jayadev, Anthuan Ferino-Perez, Florian Matz, Anna I. Krylov, Jagau Thomas-C.
Summary: We conducted an ab initio computational study on the Auger electron spectrum of benzene. Using coupled-cluster theory and equation-of-motion coupled-cluster theory, we described the decaying nature of core-ionized states through two approaches and found that the computed spectra from both approaches agreed well with experimental Auger spectra. The Auger spectrum of benzene exhibits well-resolved peaks above 260 eV corresponding to final states with electrons removed from the highest occupied molecular orbitals.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Michael Epshtein, Bruno Nunes Cabral Tenorio, Marta L. Vidal, Valeriu Scutelnic, Zheyue Yang, Tian Xue, Anna I. Krylov, Sonia Coriani, Stephen R. Leone
Summary: Tabletop X-ray spectroscopy measurements and ab initio calculations are used to investigate the influence of the bromine atom on carbon core-valence transitions in the bromobenzene cation. The results show that replacing a hydrogen atom with a bromine atom in benzene shifts the transition energy in the X-ray spectrum. Moreover, the X-ray spectrum of the bromobenzene cation is dominated by two intense transitions, which are enhanced compared to the neutral bromobenzene.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Ronit Sarangi, Kaushik D. Nanda, Anna I. Krylov
Summary: This computational study investigates the charge-transfer-to-solvent (CTTS) states of aqueous thiocyanate anion using equation-of-motion coupled-cluster methods and electrostatic embedding QM/MM scheme. The results from classical molecular dynamics (MD) and QM/MM ab initio molecular dynamics (AIMD) simulations show significant differences in the local structure around solvated SCN-. The sensitivity of the CTTS states to the solvent structure suggests that CTTS-based spectroscopy can be used to assess the quality of force-fields and density functionals. By combining CTTS-based spectroscopy with theoretical modeling, detailed microscopic information of the solvent structure can be obtained.
Article
Chemistry, Physical
Bidyut Kumar Kundu, Chuang Han, Prasenjit Srivastava, Siddhant Nagar, Katie E. E. White, Jeanette A. A. Krause, Christopher G. G. Elles, Yujie Sun
Summary: A metal-free organic photocatalyst, dBIP-OMe, was reported for the photocatalytic trifluoromethylation of alkenes without the use of sacrificial reagents. Mechanistic studies revealed two consecutive single-electron-transfer reactions between dBIP-OMe, CF3 precursor, and the alkene substrate. The trifluoromethylative bifunctionalization strategy using dBIP-OMe was applicable for both aryl and aliphatic alkenes, and various nucleophiles could be easily incorporated into the carbocation intermediate, broadening the application scope of this photocatalytic method.
Article
Chemistry, Analytical
Prasenjit Srivastava, David A. Stierwalt, Christopher G. Elles
Summary: Two-photon absorption (2PA) spectroscopy is used to study the nonlinear properties of molecules. A broadband 2PA spectroscopy using a pump-probe approach is proposed to obtain a continuous 2PA spectrum without tuning the excitation laser. This research demonstrates the use of stimulated Raman scattering as an internal standard to accurately measure absolute 2PA cross sections.
ANALYTICAL CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Sarah Loeffelsender, Pierre Beaujean, Marc de Wergifosse
Summary: This review presents the theoretical background of simplified quantum chemistry methods for computing non-linear optical properties and their applications in large systems. It outlines methods used for computing ground states of large systems, specifically the xTB scheme. The article also provides an overview of approaches to compute excited states and response properties, with emphasis on the simplified time-dependent density functional theory (sTD-DFT). Recent applications of sQC methods, particularly the sTD-DFT scheme, to large challenging systems are showcased. The review concludes by summarizing current and future method developments in the sQC framework.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2023)
