The generalized oscillator strengths of the dipole-forbidden excitations of the ^(1)A_(2) of H_(2)O and D_(2)O were calculated with the time dependent density functional theory,by taking into account the vibronic effe...The generalized oscillator strengths of the dipole-forbidden excitations of the ^(1)A_(2) of H_(2)O and D_(2)O were calculated with the time dependent density functional theory,by taking into account the vibronic effect.It is found that the vibronic effect converts the dipole-forbidden excitation of the ^(1)A_(2) into a dipole-allowed one,which enhances the intensities of the corresponding generalized oscillator strength in the small squared momentum transfer region.The present investigation shows that the vibronic effect of H_(2)O is slightly stronger than that of D_(2)O,which exhibits a clear isotopic effect.展开更多
The use of cooperative vibronic spectroscopy to measure coordination numbers of the ligands surrounding rare earth ions in solutions was proposed and demonstrated. It is shown that the time-resolved cooperative vibron...The use of cooperative vibronic spectroscopy to measure coordination numbers of the ligands surrounding rare earth ions in solutions was proposed and demonstrated. It is shown that the time-resolved cooperative vibronic spectroscopy is a very useful technique for the determination of the ligand type and ligand number for different coordination groups. Coordination configuration of arginine with Tb3+ in solutions with different pH values was studied. It demonstrates that the carboxy1 of arginine can replace H2O to coordinate with Tb3+ and the coordination number of carboxyl increases with the increase of pH value of the solutions.展开更多
In this work,we demonstrate the phonon-assisted vibronic lasing of a Yb-doped sesquioxide Yb:LuScO_(3)crystal.The electron–phonon coupling process was analyzed and the Huang-Rhys factor S was calculated to be 0.75 as...In this work,we demonstrate the phonon-assisted vibronic lasing of a Yb-doped sesquioxide Yb:LuScO_(3)crystal.The electron–phonon coupling process was analyzed and the Huang-Rhys factor S was calculated to be 0.75 associated with the fluorescence spectrum at room temperature.By a rational cavity design to suppress lasing below 1100 nm,a continuously spectral tunability from 1121 to 1136 nm was realized in a Yb:LuScO_(3)laser,which represents the longest achievable wavelength in the Yb-doped sesquioxide lasers.Moreover,the Raman spectrum indicated that the Egphonon mode with a frequency of 472 cm^(-1)was mainly devoted to the phonon-assisted transition process.This work broadens the achievable laser spectrum of Yb-doped sesquioxide,and suggests that the multiphonon–electron coupling strategy should be universal for other laser materials.展开更多
We report the SERS enhancements of Raman forbidden surface modes of TiO<sub>2</sub> in different sized TiO<sub>2</sub> crystals. This current study utilizes the relationship between the vibroni...We report the SERS enhancements of Raman forbidden surface modes of TiO<sub>2</sub> in different sized TiO<sub>2</sub> crystals. This current study utilizes the relationship between the vibronic coupling and the degree of charge-transfer to explain the differences of Surface Enhanced Raman Scattering (SERS) enhancements. Our study shows a direct correlation between the degree of charge-transfer and vibronic coupling. This relationship suggests that charge-transfer between the N-719 dye and TiO<sub>2</sub> due to vibronic coupling plays a fundamental role in SERS enhancements. Furthermore, this study shows a strong dependence of the enhancements of the N-719 dye molecular modes to that of the surface modes. This indicates that the mechanism that governs the enhancements of the surface modes in TiO<sub>2</sub> crystals most likely also dictates the enhancements of the N-719 dyes.展开更多
The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all ...The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all the papers devoted to this problem, it is shown that the instability of planar configurations of heterocyclic molecules leading to symmetry breaking and distortions is induced by the pseudo Jahn-Teller effect (PJTE). Special attention in this work is paid to the mechanism of suppression and enhancement of the PJTE distortions of heterocycles by oxidation, reduction, and chemical substitutions. It is demonstrated that oxidation of 1,4-dithiine containing compounds leads to suppression of the PJTE and to restoration of their planar nuclear configurations. An example of a dibenzo[1,2]dithiine molecule is used to demonstrate the mechanism of enhancement of the PJTE by reduction. It is shown that the reduction of the neutral C12H8S2 molecule up to the dianion (C12H8S2)2- enhances the PJTE, followed by the S-S bond cleavage and significant structural distortions of the system. The change of the PJTE by chemical substitutions, accompanied either by puckering or by planarization of heterocyclic compounds, is discussed using as examples 1,4-ditinine and its S-oxygenated derivatives.展开更多
We present a study of the physical properties of the vibrational excitation in α-helicoidal macromolecular chains, caused by the interaction with acoustical and optical phonon modes. The influence of the temperature ...We present a study of the physical properties of the vibrational excitation in α-helicoidal macromolecular chains, caused by the interaction with acoustical and optical phonon modes. The influence of the temperature and the basic system parameters on the vibron dressing have been analyzed by employing the simple mean-field approach based on the variational extension of the Lang-Firsov unitary transformation. The applied approach predicts a region in system parameter space where one has an abrupt transition from a partially dressed (light and mobile) to a fully dressed (immobile) vibron state. We found that the boundary of this region depends on system temperature and the type of bond among structural elements in the macromolecular chain.展开更多
Base pair mismatch has been regarded as the main source of DNA point mutations, where minor shortlived tautomers were usually involved. However, the detection and characterization of these unnatural species pose chall...Base pair mismatch has been regarded as the main source of DNA point mutations, where minor shortlived tautomers were usually involved. However, the detection and characterization of these unnatural species pose challenges to existing techniques. Here, by using systematic structural and ultrafast resonance Raman(RR) spectral analysis for the four possible conformers of guanine-cytosine base pairs, the prominent marker Raman bands were identified. We found that the hydrogen bonding vibrational region from 2300 cm^(-1) to 3700 cm^(-1) is ideal for the identification of these short live species. The marker bands provide direct evidence for the existence of the tautomer species, thus offering an effective strategy to detect the short-lived minor species. Ultrafast resonance Raman spectroscopy would be a powerful tool to provide direct evidence of critical dynamical details of complex systems involving protonation or tautomerization.展开更多
Blue-emission(~480 nm)CsPbBr_(3) nanoparticles with ultra-small size(~2.1 nm)are synthesized using the liquid nitrogen freezing with the ligand of dodecylbenzene sulfonic acid(DBSA).Asymmetric narrow emissions at the ...Blue-emission(~480 nm)CsPbBr_(3) nanoparticles with ultra-small size(~2.1 nm)are synthesized using the liquid nitrogen freezing with the ligand of dodecylbenzene sulfonic acid(DBSA).Asymmetric narrow emissions at the low energy side,with the full width at half-maximum of~20 nm,are observed in solution and film at room temperature.The spectral asymmetry is mainly ascribed to phonon vibronic replica with averaged phonon energy of~40 meV.Moreover,exciting this CsPbBr_(3) nanoparticles solution using linearly polarized 6 ns pulsed laser at 355 nm,we observe polarized emission with polarization degree(P_(PL))of~7%,and P_(PL) decreases more than 20%in the vibronic progression.However,the P_(PL) goes to zero in frozen solutions as well as in films.Thus we speculate the polarized emission is due to the photoinduced re-alignment of nanoparticles,and the diminished P_(PL) at the phonon side band may be due to the non-adiabatic electronic-to-vibronic transitions.The novel phenomena from the ultra-small CsPbBr_(3) nanoparticle demonstrated in this work may provide fundamental insights into its photophysics with direct implications for optoelectronics.展开更多
The investigation of electronic excited states in single-molecule junctions not only provides platforms to reveal the photophysical and photochemical processes at the molecular level,but also brings opportunities for ...The investigation of electronic excited states in single-molecule junctions not only provides platforms to reveal the photophysical and photochemical processes at the molecular level,but also brings opportunities for the development of single-molecule optoelectronic devices.Understanding the interaction mechanisms between molecules and nanocavities is essential to obtain ondemand properties in devices by artificial design,since molecules in junctions exhibit unique behaviors of excited states benefited from the structures of metallic nanocavities.Here,we review the excitation mechanisms involved in the interplay between molecules and plasmonic nanocavities,and reveal the influence of nanostructures on excited-state properties by demonstrating the differences in excited state decay processes.Furthermore,vibronic transitions of molecules between nanoelectrodes are also discussed,offering a new single-molecule characterization method.Finally,we provide the potential applications and challenges in single-molecule optoelectronic devices and the possible directions in exploring the underlying mechanisms of photophysical and photochemical processes.展开更多
Acryloyl fluoride is an ideal molecule for investigating the phenomenon of hindered internal rotation.In concert with recently acquired high-resolution UV absorption spectrum of acryloyl fluoride,in this study,the abs...Acryloyl fluoride is an ideal molecule for investigating the phenomenon of hindered internal rotation.In concert with recently acquired high-resolution UV absorption spectrum of acryloyl fluoride,in this study,the absorption spectra of the s-trans and s-cis isomers of acryloyl fluoride were theoretically simulated.The simulated spectra were convoluted by a Gaussian function with displacement,distortion,Franck-Condon,Herzberg-Teller,and Duschinsky effects in the framework of the time-independent model.The statistical vibronic transition analysis reveals the unity of the spectrum transition property,the relevant normal modes,and the primary geometrical variations,enriching the understanding of the experimental observation.The discrepancy between the theoretical and experimental spectra was interpreted clearly.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12334010,12174259,and 11604003)。
文摘The generalized oscillator strengths of the dipole-forbidden excitations of the ^(1)A_(2) of H_(2)O and D_(2)O were calculated with the time dependent density functional theory,by taking into account the vibronic effect.It is found that the vibronic effect converts the dipole-forbidden excitation of the ^(1)A_(2) into a dipole-allowed one,which enhances the intensities of the corresponding generalized oscillator strength in the small squared momentum transfer region.The present investigation shows that the vibronic effect of H_(2)O is slightly stronger than that of D_(2)O,which exhibits a clear isotopic effect.
基金the Natural Science Foundation of Guangdong Province!980278, 960036the National Natural Science Foundation of China!29705004
文摘The use of cooperative vibronic spectroscopy to measure coordination numbers of the ligands surrounding rare earth ions in solutions was proposed and demonstrated. It is shown that the time-resolved cooperative vibronic spectroscopy is a very useful technique for the determination of the ligand type and ligand number for different coordination groups. Coordination configuration of arginine with Tb3+ in solutions with different pH values was studied. It demonstrates that the carboxy1 of arginine can replace H2O to coordinate with Tb3+ and the coordination number of carboxyl increases with the increase of pH value of the solutions.
基金supported by the National Key Research and Development Program of China(Nos.2021YFB3601504 and 2021YFA0717800)the National Natural Science Foundation of China(Nos.52002220,92163207,52025021,and 51890863)the Future Plans of Young Scholars at Shandong University。
文摘In this work,we demonstrate the phonon-assisted vibronic lasing of a Yb-doped sesquioxide Yb:LuScO_(3)crystal.The electron–phonon coupling process was analyzed and the Huang-Rhys factor S was calculated to be 0.75 associated with the fluorescence spectrum at room temperature.By a rational cavity design to suppress lasing below 1100 nm,a continuously spectral tunability from 1121 to 1136 nm was realized in a Yb:LuScO_(3)laser,which represents the longest achievable wavelength in the Yb-doped sesquioxide lasers.Moreover,the Raman spectrum indicated that the Egphonon mode with a frequency of 472 cm^(-1)was mainly devoted to the phonon-assisted transition process.This work broadens the achievable laser spectrum of Yb-doped sesquioxide,and suggests that the multiphonon–electron coupling strategy should be universal for other laser materials.
文摘We report the SERS enhancements of Raman forbidden surface modes of TiO<sub>2</sub> in different sized TiO<sub>2</sub> crystals. This current study utilizes the relationship between the vibronic coupling and the degree of charge-transfer to explain the differences of Surface Enhanced Raman Scattering (SERS) enhancements. Our study shows a direct correlation between the degree of charge-transfer and vibronic coupling. This relationship suggests that charge-transfer between the N-719 dye and TiO<sub>2</sub> due to vibronic coupling plays a fundamental role in SERS enhancements. Furthermore, this study shows a strong dependence of the enhancements of the N-719 dye molecular modes to that of the surface modes. This indicates that the mechanism that governs the enhancements of the surface modes in TiO<sub>2</sub> crystals most likely also dictates the enhancements of the N-719 dyes.
文摘The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all the papers devoted to this problem, it is shown that the instability of planar configurations of heterocyclic molecules leading to symmetry breaking and distortions is induced by the pseudo Jahn-Teller effect (PJTE). Special attention in this work is paid to the mechanism of suppression and enhancement of the PJTE distortions of heterocycles by oxidation, reduction, and chemical substitutions. It is demonstrated that oxidation of 1,4-dithiine containing compounds leads to suppression of the PJTE and to restoration of their planar nuclear configurations. An example of a dibenzo[1,2]dithiine molecule is used to demonstrate the mechanism of enhancement of the PJTE by reduction. It is shown that the reduction of the neutral C12H8S2 molecule up to the dianion (C12H8S2)2- enhances the PJTE, followed by the S-S bond cleavage and significant structural distortions of the system. The change of the PJTE by chemical substitutions, accompanied either by puckering or by planarization of heterocyclic compounds, is discussed using as examples 1,4-ditinine and its S-oxygenated derivatives.
基金supported by the Science Fund of the Ministry of Education and Science of Republic of Serbia (Grant Nos. III–45005 and III–45010)by the Project within the Cooperation Agreement between the JINR, Dubna, Russian FederationMinistry of Education and Science of Republic of Serbia
文摘We present a study of the physical properties of the vibrational excitation in α-helicoidal macromolecular chains, caused by the interaction with acoustical and optical phonon modes. The influence of the temperature and the basic system parameters on the vibron dressing have been analyzed by employing the simple mean-field approach based on the variational extension of the Lang-Firsov unitary transformation. The applied approach predicts a region in system parameter space where one has an abrupt transition from a partially dressed (light and mobile) to a fully dressed (immobile) vibron state. We found that the boundary of this region depends on system temperature and the type of bond among structural elements in the macromolecular chain.
基金the financial support from the National Key Research and Development Program of China(No.2019YFA0708703)the National Natural Science Foundation of China(NSFC,No.21773309)+3 种基金the High-level Science Foundation of Qingdao Agricultural University(No.663/1114351)the Hefei National Laboratory for Physical Sciences at the Microscale(No.KF2020004)Xiangyang Science and Technology Research and Development(No.2020YL09)Hubei University of Arts and Science(Nos.HLOM222003,2020kypytd002)。
文摘Base pair mismatch has been regarded as the main source of DNA point mutations, where minor shortlived tautomers were usually involved. However, the detection and characterization of these unnatural species pose challenges to existing techniques. Here, by using systematic structural and ultrafast resonance Raman(RR) spectral analysis for the four possible conformers of guanine-cytosine base pairs, the prominent marker Raman bands were identified. We found that the hydrogen bonding vibrational region from 2300 cm^(-1) to 3700 cm^(-1) is ideal for the identification of these short live species. The marker bands provide direct evidence for the existence of the tautomer species, thus offering an effective strategy to detect the short-lived minor species. Ultrafast resonance Raman spectroscopy would be a powerful tool to provide direct evidence of critical dynamical details of complex systems involving protonation or tautomerization.
基金supported by startup funding at Fudan University,National Natural Science Foundation of China (Nos.62074079,61774039)large instrument equipment open fund of Nanjing University of Science and Technology.
文摘Blue-emission(~480 nm)CsPbBr_(3) nanoparticles with ultra-small size(~2.1 nm)are synthesized using the liquid nitrogen freezing with the ligand of dodecylbenzene sulfonic acid(DBSA).Asymmetric narrow emissions at the low energy side,with the full width at half-maximum of~20 nm,are observed in solution and film at room temperature.The spectral asymmetry is mainly ascribed to phonon vibronic replica with averaged phonon energy of~40 meV.Moreover,exciting this CsPbBr_(3) nanoparticles solution using linearly polarized 6 ns pulsed laser at 355 nm,we observe polarized emission with polarization degree(P_(PL))of~7%,and P_(PL) decreases more than 20%in the vibronic progression.However,the P_(PL) goes to zero in frozen solutions as well as in films.Thus we speculate the polarized emission is due to the photoinduced re-alignment of nanoparticles,and the diminished P_(PL) at the phonon side band may be due to the non-adiabatic electronic-to-vibronic transitions.The novel phenomena from the ultra-small CsPbBr_(3) nanoparticle demonstrated in this work may provide fundamental insights into its photophysics with direct implications for optoelectronics.
基金supported by the National Natural ScienceFoundation of China (Nos. 22173075, 21933012 and 31871877)the National Key R&D Program of China (No. 2017YFA0204902)+1 种基金the Fundamental Research Funds for the Central Universities(Nos. 20720200068 and 20720190002)the Beijing NationalLaboratory for Molecular Sciences (No. BNLMS202005).
文摘The investigation of electronic excited states in single-molecule junctions not only provides platforms to reveal the photophysical and photochemical processes at the molecular level,but also brings opportunities for the development of single-molecule optoelectronic devices.Understanding the interaction mechanisms between molecules and nanocavities is essential to obtain ondemand properties in devices by artificial design,since molecules in junctions exhibit unique behaviors of excited states benefited from the structures of metallic nanocavities.Here,we review the excitation mechanisms involved in the interplay between molecules and plasmonic nanocavities,and reveal the influence of nanostructures on excited-state properties by demonstrating the differences in excited state decay processes.Furthermore,vibronic transitions of molecules between nanoelectrodes are also discussed,offering a new single-molecule characterization method.Finally,we provide the potential applications and challenges in single-molecule optoelectronic devices and the possible directions in exploring the underlying mechanisms of photophysical and photochemical processes.
文摘Acryloyl fluoride is an ideal molecule for investigating the phenomenon of hindered internal rotation.In concert with recently acquired high-resolution UV absorption spectrum of acryloyl fluoride,in this study,the absorption spectra of the s-trans and s-cis isomers of acryloyl fluoride were theoretically simulated.The simulated spectra were convoluted by a Gaussian function with displacement,distortion,Franck-Condon,Herzberg-Teller,and Duschinsky effects in the framework of the time-independent model.The statistical vibronic transition analysis reveals the unity of the spectrum transition property,the relevant normal modes,and the primary geometrical variations,enriching the understanding of the experimental observation.The discrepancy between the theoretical and experimental spectra was interpreted clearly.