Article
Chemistry, Physical
Tatsuya Yoshida, Kazuya Watanabe
Summary: The spectral diffusion of molecular excitons in thin films of 3,4,9,10-perylenetetracarboxylic-diimide was studied using two-dimensional electronic spectroscopy (2DES) in this work. The temperature dependence of the spectral diffusion was analyzed by studying the center line slope (CLS) of the ground-state bleach in the 2DES signal, revealing a significant acceleration of the decay of the CLS with increasing temperature. An anharmonic coupling model was proposed to explain this phenomenon, suggesting that exciton energy gap fluctuations are enhanced by coupling with low-frequency phonon modes.
JOURNAL OF PHYSICAL CHEMISTRY B
(2021)
Article
Chemistry, Physical
Xiongwei Guo, Xinlu Cheng, Hong Zhang
Summary: Controlling the optical properties of light-responsive organic molecules is essential for their application in photonics. We demonstrate how light-responsive organic polaritons formed inside an optical cavity can be used to modify these properties based on first principles. Our results show that the cavity can modulate the dispersion and absorption properties of organic molecules, and the strong light-matter coupling has the potential to manipulate the optical dipole trap and spectral features of the molecules. Moreover, we find that the cavity can also control the spontaneous radiation of the molecules via the Purcell effect.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Haris Habib, Wenjing Zhao, Sibgha Mir, Liang Ma, Guangjun Tian
Summary: In this study, the influence of lanthanide (LN) doping on the electronic, magnetic and optical properties of HfSe2 monolayer was investigated using density functional theory calculations. The results showed that LN doping can alter the ground states of HfSe2 monolayers, where five dopants (La, Nd, Eu, Tm, and Lu) led to the formation of metallic ground states, while Ce and Pr doping maintained the semiconductor properties. Spin polarized calculations revealed that Nd, Eu, Tm, and Pr doping resulted in nonzero magnetic moment, attributed to unpaired f-electrons. Additionally, the LN-doped HfSe2 monolayers with metallic ground states demonstrated enhanced absorption abilities in the infrared region, indicating potential applications in solar energy harvesting. These findings not only demonstrated the possibility of modulating the electronic, magnetic, and optical properties of HfSe2 monolayers through LN doping, but also suggested the application potential of such systems in spintronics, nanoelectronics, and optoelectronics.
RESULTS IN PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Lei Lu, Wenjing Zhang, Yujing Yang, Jianping Zhang, Gengwen Yin, Xiuping Wang, Yuedong Yang, Wenlong Hou, Haiquan Zhang
Summary: Heterojunctions of PTCDI nanosheets coupled with Sb2S3 nanorods were successfully synthesized using a two-step electrodeposition method. The addition of Sb2S3 significantly enhanced the stability of PTCDI, which already exhibited excellent sensing properties for hydrazine. The resulting PTCDI/Sb2S3 composite nanomaterials showed high electrocatalytic performance and exhibited outstanding analytical performance for the detection of hydrazine.
Article
Optics
Xue Bai, Qi Jiang, Pei Song, Ze-Peng Jia, Sen Lu, Zhi-Kai Gao, Shao-Hua Lan, Hong Cui, Rong Feng, Zhi-Yong Liang, Qin Kang, Hong-Kuan Yuan
Summary: This study found that a vertical electric field helps to maintain the thermodynamic and kinetic stability of monolayer CdI2, leading to the development of a Mexican-hat electronic state and a giant Stark effect. The electric field induces strong spin polarization, causing energy level splitting and spin flipping in the valence band. Additionally, the electric field broadens the optical response range and diminishes the excitonic effect in monolayer CdI2.
Article
Chemistry, Multidisciplinary
Fan Jin, Zhichao Zhao
Summary: The reconstructed shape of the anatase (001) surface is not relevant to its high reactivity, with both the unreconstructed surface and ADM surface showing high reactivity towards dissociating water molecules. Additionally, the internal atomic layer structure of the ADM surface is unfavorable for hole transfer.
Article
Engineering, Multidisciplinary
Chengguo Jin, Lifeng Liu
Summary: The Se-doping can improve the performance of MnTeMoO6 crystal by enhancing its structural stability and laser damage threshold. However, it also leads to a decrease in the transmission ability of the crystal in the visible region, thus affecting the laser frequency conversion efficiency.
ALEXANDRIA ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Eleonora Pavoni, Mircea Gabriel Modreanu, Elaheh Mohebbi, Davide Mencarelli, Pierluigi Stipa, Emiliano Laudadio, Luca Pierantoni
Summary: In this study, the electronic and optical properties of MoO3 and MoO2 were investigated using Density Functional Theory calculations. The Meta Generalized Gradient Approximation (MGGA) SCAN functional and PseudoDojo pseudopotential were used for the first time to understand the nature of different Mo-O bonds in these materials. The calculated density of states, band structure, and optical properties were validated with experimental results, showing that the proposed theoretical techniques accurately reproduce the properties of both MoO2 and MoO3 systems.
Article
Materials Science, Multidisciplinary
Weiguo Jing, Mingzhe Liu, Jun Wen, Lixin Ning, Min Yin, Chang-Kui Duan
Summary: Eliminating residual infrared absorption in titanium sapphire remains a crucial task. Our research provides a comprehensive understanding of the formation of various potentially significant defects and complexes, as well as their dependence on processing conditions.
Article
Chemistry, Physical
Yaming Zhang, Wuduan Zhao, Jun Lu, Yunfeng Zhang, Haibao Zhang, Xiaojun Li
Summary: Graphdiyne (GDY) is a promising two-dimensional carbon material with unique structural features. In this study, a series of AuGen-GDY complexes were designed and systematically studied. The adsorption of endohedral AuGen clusters on GDY surface was found to be stable, and the electronic and optical properties of the complexes were analyzed. This study highlights the importance of endohedral cluster adsorption on GDY surface and provides insights for the synthesis of novel GDY-based cluster-assembled materials.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Physical
Theo Cavignac, Stephane Jobic, Camille Latouche
Summary: In this study, a methodology based on constrained density functional theory and vibrational mode computations is presented to simulate and interpret the luminescence spectra of periodic solids. By combining electronic and vibrational contributions, an overall vibrationally resolved emission spectrum is accurately reproduced for Ti-doped BaZrO3, allowing for an unambiguous assignment of the observed luminescence to a Ti3+ + O- -> Ti4+ + O2- charge transfer.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Physics, Multidisciplinary
Fangzhou Zhao, Mark E. Turiansky, Audrius Alkauskas, Chris G. Van de Walle
Summary: Trap-assisted Auger-Meitner recombination is highlighted as a dominant nonradiative process in wide-band-gap materials, and a first-principles methodology is presented to determine the rates of this process in semiconductors or insulators due to defects or impurities.
PHYSICAL REVIEW LETTERS
(2023)
Article
Optics
Changiz Vatankhah, Hojat Allah Badehian
Summary: The electronic band gap and optical spectra of armchair silicon carbide nanotubes were studied using DFT and NEGF methods, with SiCNTs (11, 11) found to have the largest band gap. The refractive index of SiCNTs (9, 9) peaked at energies below 2.5 eV, with optical absorption occurring in the 2-5 eV range for z polarization. Additionally, SiCNTs with larger diameters exhibited smaller first optical band gaps.
Article
Engineering, Electrical & Electronic
Wei Zheng, Qi-Jun Liu, Zheng-Tang Liu, Zheng-Quan Zhang
Summary: In this study, the structural, electronic properties, and Raman spectra of different carbon allotropes under pressure were investigated using first-principles calculations. The results showed that pressure had a significant effect on the Raman spectra but had minimal impact on the structural and electronic properties. Additionally, the elastic and thermal properties at zero pressure were also studied, and the obtained values were comparable to those of diamond.
MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING
(2022)
Article
Chemistry, Physical
Jutao Hu, Jinjing Zhang, Haiyan Xiao, Lei Xie, Guangai Sun, Huahai Shen, Pengcheng Li, Jianwei Zhang, Xiaotao Zu
Summary: This study investigated the hydrogen storage properties of high entropy alloy TiZrVMoNb using density functional theory calculations. The results showed that it has a high hydrogen storage capacity and moderate hydrogen desorption temperature, indicating great potential as hydrogen storage materials.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Chemistry, Multidisciplinary
Tarcius N. Ramos, Benoit Champagne
Summary: The Sequential Quantum Mechanics/Molecular Mechanics scheme was used to systematically investigate the polarizability and first hyperpolarizability at the water-vacuum interface. It was found that the anisotropy of the polarizability increased, and there was an increase in the response of the first hyperpolarizability.
Article
Chemistry, Multidisciplinary
Bethany R. R. Hood, Yovan de Coene, Afonso V. V. Torre Do Vale Froes, Claire F. F. Jones, Pierre Beaujean, Vincent Liegeois, Fraser MacMillan, Benoit Champagne, Koen Clays, John Fielden
Summary: Electrochemically switched 2(nd) order non-linear optical responses have been demonstrated for the first time in polyoxometalates (POMs), with an arylimido-derivative showing a leading combination of high on/off contrast (94 %), high visible transparency, and cyclability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Francois Mairesse, Lorenzo Maschio, Benoit Champagne
Summary: Using the CRYSTAL17 package, first-principles calculations were conducted to predict the values of chi((2)) for six historical NLO crystals. Various computational aspects were considered to ensure converged results, including lattice summations, k-points, electrostatic interactions, and atomic basis set size. The impact of HF exchange on the chi((2)) tensor components was also investigated.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Charlotte Bouquiaux, Frederic Castet, Benoit Champagne
Summary: The extensive collection of lipids found in cell membranes plays a significant role in the overall structure, dynamics, and properties of the membranes, as well as the biological processes occurring within them. This study focuses on investigating a range of saturated glycerophospholipids with varying headgroup structures using second harmonic generation (SHG) nonlinear optical (NLO) response analysis. The research reveals that the lipidic arrangement is strongly influenced by the hydrophilic head, while the hydrophobic region has less impact. Moreover, the computational approach provides insights into the relationship between lipid building blocks and the NLO responses of the embedded dye.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Organic
Abel Idrice Adjieufack, Benoit Champagne, Vincent Liegeois
Summary: Bonding evolution theory was used to elucidate the reaction mechanism of the intramolecular aza-Wittig reaction. The reaction involves the formation of a cycloadduct, decarboxylation, intramolecular [2+2] cycloaddition, and retro [2+2] cycloaddition. The rate-determining step is the formation of the cycloadduct and the reaction is exergonic, resulting in the formation of the aromatic benzothiazole.
SYNTHESIS-STUTTGART
(2023)
Editorial Material
Chemistry, Multidisciplinary
Tarcius N. Ramos, Benoit Champagne
Summary: This article investigates the interfacial selectivity of second harmonic generation at the water-vacuum interface through combining classical molecular dynamics and quantum chemistry simulations, distinguishing between bulk and interfacial contributions through calculated molecular first hyperpolarizability responses.
Article
Chemistry, Physical
Tarcius N. Ramos, Laura Le Bras, Yves L. Dory, Benoit Champagne
Summary: Targeting the use of second harmonic generation (SHG) as a bioimaging technique, the SHG first hyperpolarizabilities (beta) of assemblies of benzene-1,3,5-tricarboxamide derivatives were evaluated using density functional theory. The calculations revealed that the assemblies exhibit size-dependent SHG responses, with a maximum 18-times increase in beta HRS for B4 when going from monomer to pentamer. The presence of iodine atoms on the phenyl core enhanced the intrinsic SHG responses, and the side chains affected the relative orientation of dipole moment and first hyperpolarizability vectors.
Article
Chemistry, Physical
Andrea Bonvicini, Kayn A. Forbes, David L. Andrews, Benoit Champagne
Summary: This study presents the first computational quantum-chemistry implementation of hyper-Rayleigh scattering optical activity (HRS-OA), a nonlinear chiroptical phenomenon. The equations for simulating the differential scattering ratios of HRS-OA are derived based on the theory of quantum electrodynamics and the interactions of electric dipole, magnetic dipole, and electric quadrupole. Computation results of HRS-OA quantities for a chiral organic molecule (methyloxirane) using a broad range of atomic orbital basis sets are presented and analyzed, demonstrating the ability of HRS-OA to distinguish between enantiomers of the same chiral molecule.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Francois Mairesse, Benoit Champagne
Summary: The quantum treatment of electrons at the Kohn-Sham Density Functional Theory (DFT) level of approximation is used to optimize the structure of four organic and organo-metallic crystalline systems with nonlinear optical properties. The study addresses the lack of London-type interactions description in exchange-correlation functionals (XCFs) by employing the D* scheme, a variation of the D2 correction scaled for crystal solid state interactions. The performance and suitable scaling factors of the D* scheme are demonstrated for four representative XCFs.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2023)
Article
Chemistry, Physical
Komlanvi Sevi Kaka, Pierre Beaujean, Frederic Castet, Benoit Champagne
Summary: Recent measurements of the third harmonic scattering responses of molecules have provided new insights into computing molecular second hyperpolarizabilities (gamma) and deducing structure-property relationships. This paper evaluates the second hyperpolarizability of the pi-nitroaniline molecule using various wavefunction and density functional theory methods. The results show that the MP2 scheme offers the best accuracy/cost ratio for computing static gamma, while density functional theory methods still face challenges in accurately computing gamma. Additionally, the double-hybrid B2-PLYP functional provides accurate estimates of static gamma values.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Andrea Bonvicini, Benoit Champagne
Summary: In this work, the expressions for the third-harmonic scattering optical activity (THS-OA) spectroscopic responses are derived by combining molecular quantum electrodynamics (QED) and response theory, allowing for their computational implementation. The study shows how the pure and mixed second hyperpolarizabilities can be obtained as specific cases of a generic cubic response function, enabling the calculation of THS-OA spectroscopy.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Andrea Bonvicini, Benoit Champagne
Summary: This paper discusses the theoretical formulation and computational procedure of linear and nonlinear molecular spectroscopies applied to isotropic samples. It introduces the concept of rotational averaging of Cartesian tensors and proposes a heuristic computational method for finding linearly independent fundamental isotropic Cartesian tensors.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Carmelo Naim, Raphael Vangheluwe, Isabelle Ledoux-Rak, Benoit Champagne, Claire Tonnele, Mireille Blanchard-Desce, Eduard Matito, Frederic Castet
Summary: The second-order nonlinear optical properties of four series of amphiphilic cationic chromophores have been investigated experimentally and theoretically. The theoretical methodology combining classical molecular dynamics and quantum chemical calculations provides a rational approach for designing SHG dyes based on EFISH measurements. The good agreement between experimental and theoretical results demonstrates the usefulness of this MD + QM scheme.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Charlotte Bouquiaux, Frederic Castet, Benoit Champagne
Summary: Lipid molecules play important roles in cell functions and their structural diversity is related to different fatty acids. The nature of fatty acids has an additive effect on the overall membrane structure. Nonlinear optical responses of an embedded chromophore can be used to study the local structure of cell membranes.
Article
Chemistry, Physical
Charlotte Bouquiaux, Pierre Beaujean, Tarcius N. Ramos, Frederic Castet, Vincent Rodriguez, Benoit Champagne
Summary: The solvent effects on the optical properties of an ANEP dye were studied using experimental and theoretical methods. Experimental measurements showed a decrease in the hyperpolarizablity of the dye in polar solvents, which was confirmed by theoretical calculations using different solvation models.
JOURNAL OF CHEMICAL PHYSICS
(2023)