The A-band resonance Raman spectra of thiourea were obtained in water and acetonitrile solution. B3LYP/6-311＋＋G（3df,3pd） and RCIS/6-311＋＋G（3df,3pd） calculations were done to elucidate the ultraviolet electroni...The A-band resonance Raman spectra of thiourea were obtained in water and acetonitrile solution. B3LYP/6-311＋＋G（3df,3pd） and RCIS/6-311＋＋G（3df,3pd） calculations were done to elucidate the ultraviolet electronic transitions, the distorted geometry structure and the saddle point of thiourea in 21A excited state, respectively. The resonance Raman spectra were assigned. The absorption spectrum and resonance Raman intensities were modeled using Heller＇s time-dependent wavepacket approach to resonance Raman scattering. The results indicate that largest change in the displacement takes place with the C--S stretch mode u6 （｜△｜=0.95） and noticeable changes appear in the H5N3H6＋H8N4H7 wag v5 （｜△｜=0.19）, NCN symmetric stretch^-C--S stretch＋N3H6＋H8N4 wag v4 （｜△｜=0.18）, while the moderate intensities of 2-15 and 4-15 are mostly due to the large excited state frequency changes of v15, but not due to its significant change in the normal mode displacement. The mechanism of the appearance of even overtones of the S-CN2 out of plane deformation is explored. The results indicate that a Franck-Condon region saddle point is the driving force for the quadric phonon mechanism within the standard A-term of resonance Raman scattering, which leads to the pyramidalization of the carbon center and the geometry distortion of thiourea molecule in 21A excited state.展开更多
Raman(resonance Raman,FT-Raman),IR and UV-visible spectroscopy and quantum chemistry calculations were used to investigate the photodissociation dynamics of furfural in S2 state.The resonance Raman(RR)spectra indicate...Raman(resonance Raman,FT-Raman),IR and UV-visible spectroscopy and quantum chemistry calculations were used to investigate the photodissociation dynamics of furfural in S2 state.The resonance Raman(RR)spectra indicate that the photorelaxation dynamics for the S0→S2 excited state is predominantly along nine motions:C=O stretchν5(1667 cm-1),ring C=C antisymmetric stretchν6(1570 cm-1),ring C=C symmetric stretchν7(1472 cm-1),C2-O6-C5 symmetric stretch/C1-H8 rock in planeν8(1389 cm-1),C3-C4 stretch/C1-H8 rock in planeν9(1370 cm-1),C5-O6 stretch in planeν12(1154 cm-1),ring breathν13(1077 cm-1),C3-C4 stretchν14(1020 cm-1),C3-C2-O6 symmetric stretchν16(928 cm-1).Stable structures of S0,S1,S2,T1 and T2 states with Cs point group were optimized at CASSCF method in Franck-Condon region there are S2/S1 conical intersection was found by state average method and RR spectra.展开更多
Based on the scheme of damped harmonic oscillator quantization and thermo-field dynamics （TFD）, the quantization of mesoscopic damped double resonance RLC circuit with mutual capacitance-inductance coupling is propo...Based on the scheme of damped harmonic oscillator quantization and thermo-field dynamics （TFD）, the quantization of mesoscopic damped double resonance RLC circuit with mutual capacitance-inductance coupling is proposed. The quantum fluctuations of charge and current of each loop in a squeezed vacuum state are studied in the thermal excitation case. It is shown that the fluctuations not only depend on circuit inherent parameters, but also rely on excitation quantum number and squeezing parameter. Moreover, due to the finite environmental temperature and damped resistance, the fluctuations increase with the temperature rising, and decay with time.展开更多
The photophysics of 3-dimethylamino-2-methyl-propenal （DMAMP） after excitation to the S2 （ππ^＊） electronic state was studied using the resonance Raman spectroscopy and complete active space self-consistent fiel...The photophysics of 3-dimethylamino-2-methyl-propenal （DMAMP） after excitation to the S2 （ππ^＊） electronic state was studied using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The transition barriers of the ground state tautomerization reactions between DMAMP and its three isomers were determined at B3LYP/6-311＋＋G（d,p） level of theory. The vibrational spectra were assigned. The A- band resonance Raman spectra were obtained in acetonitrile with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of DMAMP. The B3LYP-TD computation was carried out to determine the relative A-band resonance Raman intensities of the fundamental modes, and the result indicated that the vibronic-coupling existed in Franck-Condon region. Complete active space self-consistent field （CASSCF） calculations were carried out to determine the excitation energies of the lower-lying singlet and triplet excited states, the conical intersection points and the intersystem crossing points. The A-band short-time structural dynamics and the corresponding decay dynamics of DMAMP were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. It was found that a sudden de-conjugation between C1=O6 and C2=C3 occurred at the Franck-Condon region of the S2（ππ^＊） state, while the enhancement of the conjugation interaction between C3 and N（CH3）2, and between C1 and C2 evolutions shortly after the wavepacket leaves away the Pranck-Condon region via the excited state charge redistribution. The de-conjugation interaction between C1=O6 and C2=C3 made the rotation of C3=N（CH3）2 group around the C2-C3 bond much easier, while the enhanced conjugation between C1 and C2, and between C3 and N（CH3）2 made the rotation around the C1-C2 bond and C3-N5 more difficult. It was revealed that the initial structural dynamics of DMAMP was predominantly towards the CI-I（S2/S0） point, while the opportunities towards either CI-2（S2/S0） or CI-3（S2/S0） point were negligible. Two decay channels of DMAMP from S2,FC（ππ^＊） to So or Tl,min via various CIs and ISCs were proposed.展开更多
Multiphoton resonant excitation and frustrated tunneling ionization,manifesting the photonic and optical nature of the driving light via direct excitation and electron recapture,respectively,are complementary mechanis...Multiphoton resonant excitation and frustrated tunneling ionization,manifesting the photonic and optical nature of the driving light via direct excitation and electron recapture,respectively,are complementary mechanisms to access Rydberg state excitation(RSE)of atoms and molecules in an intense laser field.However,clear identification and manipulation of their individual contributions in the light-induced RSE process remain experimentally challenging.Here,we bridge this gap by exploring the dissociative and nondissociative RSE of H2 molecules using bicircular two-color laser pulses.Depending on the relative field strength and polarization helicity of the two colors,the RSE probability can be boosted by more than one order of magnitude by exploiting the laser waveform-dependent field effect.The role of the photon effect is readily strengthened with increasing relative strength of the second-harmonic field of the two colors regardless of the polarization helicity.As compared to the nondissociative RSE forming H2,the field effect in producing the dissociative RSE channel of eHt;HT is moderately suppressed,which is primarily accessed via a three-step sequential process separated by molecular bond stretching.Our work paves the way toward a comprehensive understanding of the interplay of the underlying field and photon effects in the strong-field RSE process,as well as facilitating the generation of Rydberg states optimized with tailored characteristics.展开更多
High-order nonlinear multiphoton absorption is usually inefficient,but can be enhanced by designing resonant excitations between occupied and unoccupied energy levels.We conducted angle-resolved multi-photon photoemis...High-order nonlinear multiphoton absorption is usually inefficient,but can be enhanced by designing resonant excitations between occupied and unoccupied energy levels.We conducted angle-resolved multi-photon photoemission(mPPE)studies on the SnSe_(2)(001)surfaces excited by ultrashort laser pulses.By tuning photon energy and light polarization,we demonstrate the presence of a resonant four-photon photoemission(4PPE)process involving the occupied valence band(VB),the unoccupied second conduction band(CB2)and the unoccupied image-potential state(IPs)of SnSe_(2).In this 4PPE process,VB electrons of SnSe_(2) are resonantly excited into CB2 by adsorbing two photons,followed by the adsorption of another photon to populate the n=1 IPs before being emitted out to the vacuum by adsorbing one more photon.This results in a double-resonant 4PPE process,which exhibits approximately a 40 times enhancement in photoemission yields compared to cases where one of the resonant pathways,CB2→IPs,is inhibited by involving a virtual state instead of the IPs in the 4PPE.The double-resonant 4PPE process efficiently excite the bulk VB electrons outside the vacuum,like taking advantage of resonant“ladders”through two real empty electronic states of SnSe_(2).Our results highlight the important applications of mPPE in probing the band-structure,particularly the unoccupied states,of recently emerging main group dichalcogenide semiconductors.Furthermore,the discovered resonant mPPE process contributes to the exploration of their promising optoelectronic applications.展开更多
The structure and excited state properties of the H- and J-aggregates of the marine carbonyl carotenoid, fucoxanthin(Fx), were studied by various spectroscopic methods, and compared with those of Fx monomers in polar ...The structure and excited state properties of the H- and J-aggregates of the marine carbonyl carotenoid, fucoxanthin(Fx), were studied by various spectroscopic methods, and compared with those of Fx monomers in polar organic solvents. The fluorescent analysis indicated tliat the higher vibronic states of S2 contribute more to populating the S1 state, from which fluorescent emission mainly originates. Resonance Raman and density functional theory calculations confirmed the ‘card-packed' and chead-to-taiF structures of the H- and J-aggregates of Fx, respectively. An fs time-resolved absorption study proved the coexistence of Si and intramolecular charge transfer relaxation pathways upon excitation to the S2 state for both tlie monomers and aggregates.展开更多
The odd-parity high-lying states of the Sm atom are investigated systematically by a three-color resonant excitation scheme with two different excitation paths.The two intermediate states,4f 6 6s7s 7 F 0 and 4f 6 6s7s...The odd-parity high-lying states of the Sm atom are investigated systematically by a three-color resonant excitation scheme with two different excitation paths.The two intermediate states,4f 6 6s7s 7 F 0 and 4f 6 6s7s 7 F 1 are employed for paths I and II,respectively.Fifty-seven bound states are detected with paths I and II in the energy range between 44188 and 45515 cm 1,while 64 autoionizing states are found in the energy range from 45528 to 45761 cm 1.Not only the level energies of all observed states,but also the line widths of autoionizing states are determined.The possible impact of configuration interaction on the line shape of autoionizing states is also discussed.In addition,the total angular momentum is assigned uniquely to most of the states,whereas the information about the relative line intensity of all states is also presented.展开更多
A rovibrational model,including anharmonic,centrifugal,and Coriolis corrections,is used to calculate π,K,N,and ∑ orbital and radial resonances.The four orbital excitations of the n meson correspond to the/?(1235),ti...A rovibrational model,including anharmonic,centrifugal,and Coriolis corrections,is used to calculate π,K,N,and ∑ orbital and radial resonances.The four orbital excitations of the n meson correspond to the/?(1235),ti2(1670),63(2030),and π4(2250)resonances.Its first four radial excitations correspond to the π(1300),π(1800),π(2070),and 7t(2360)resonances.The orbital excitations of the K meson are interpreted as the K_(1)(1270),K_(2)(1770),K_(3)(2320),and K_(4)(2500)resonances;its radial excitations correspond to the K(1460)and K(1830)resonances.The N orbital excitations are identified with the N(1520),N(1680),N(2190),N(2220),and N(2600)resonances.The first four radial excitations of the N family correspond to the N(1440),N(1880),N(2100),and N(2300)resonances.The orbital excitations of the ∑ baryon are associated with the ∑(1670),∑(1915),∑(2100),and ∑(2250)resonances,whereas its radial excitations are identified with the ∑(1660),∑(1770),and ∑(1880)resonances.The proposed rovibrational model calculations show a good agreement with the corresponding experimental values and allow for the prediction of hadron resonances,thereby proving to be useful for the interpretation of excited hadron spectra.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.21033002 and No.20803066） and the National Basic Research Program of China （No.2007CB815203）.
文摘The A-band resonance Raman spectra of thiourea were obtained in water and acetonitrile solution. B3LYP/6-311＋＋G（3df,3pd） and RCIS/6-311＋＋G（3df,3pd） calculations were done to elucidate the ultraviolet electronic transitions, the distorted geometry structure and the saddle point of thiourea in 21A excited state, respectively. The resonance Raman spectra were assigned. The absorption spectrum and resonance Raman intensities were modeled using Heller＇s time-dependent wavepacket approach to resonance Raman scattering. The results indicate that largest change in the displacement takes place with the C--S stretch mode u6 （｜△｜=0.95） and noticeable changes appear in the H5N3H6＋H8N4H7 wag v5 （｜△｜=0.19）, NCN symmetric stretch^-C--S stretch＋N3H6＋H8N4 wag v4 （｜△｜=0.18）, while the moderate intensities of 2-15 and 4-15 are mostly due to the large excited state frequency changes of v15, but not due to its significant change in the normal mode displacement. The mechanism of the appearance of even overtones of the S-CN2 out of plane deformation is explored. The results indicate that a Franck-Condon region saddle point is the driving force for the quadric phonon mechanism within the standard A-term of resonance Raman scattering, which leads to the pyramidalization of the carbon center and the geometry distortion of thiourea molecule in 21A excited state.
基金This work was supported in parts by National Natural Science Foundation of China(No.21673208)Zhejiang Provincial Natural Science Foundation of China(No.LY16B070009).
文摘Raman(resonance Raman,FT-Raman),IR and UV-visible spectroscopy and quantum chemistry calculations were used to investigate the photodissociation dynamics of furfural in S2 state.The resonance Raman(RR)spectra indicate that the photorelaxation dynamics for the S0→S2 excited state is predominantly along nine motions:C=O stretchν5(1667 cm-1),ring C=C antisymmetric stretchν6(1570 cm-1),ring C=C symmetric stretchν7(1472 cm-1),C2-O6-C5 symmetric stretch/C1-H8 rock in planeν8(1389 cm-1),C3-C4 stretch/C1-H8 rock in planeν9(1370 cm-1),C5-O6 stretch in planeν12(1154 cm-1),ring breathν13(1077 cm-1),C3-C4 stretchν14(1020 cm-1),C3-C2-O6 symmetric stretchν16(928 cm-1).Stable structures of S0,S1,S2,T1 and T2 states with Cs point group were optimized at CASSCF method in Franck-Condon region there are S2/S1 conical intersection was found by state average method and RR spectra.
基金Project supported by the Natural Science Foundation of Heze University of Shandong Province, China （Grant No XY05WL01）, the University Experimental Technology Foundation of Shandong Province, China （Grant No S04W138）, the Natural Science Foundation of Shandong Province, China （Grant No Y2004A09） and the National Natural Science Foundation of China （Grant No 10574060）.
文摘Based on the scheme of damped harmonic oscillator quantization and thermo-field dynamics （TFD）, the quantization of mesoscopic damped double resonance RLC circuit with mutual capacitance-inductance coupling is proposed. The quantum fluctuations of charge and current of each loop in a squeezed vacuum state are studied in the thermal excitation case. It is shown that the fluctuations not only depend on circuit inherent parameters, but also rely on excitation quantum number and squeezing parameter. Moreover, due to the finite environmental temperature and damped resistance, the fluctuations increase with the temperature rising, and decay with time.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.21033002 and No.21202032） and the National Basic Research Program of China （No.2013CB834604）.
文摘The photophysics of 3-dimethylamino-2-methyl-propenal （DMAMP） after excitation to the S2 （ππ^＊） electronic state was studied using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The transition barriers of the ground state tautomerization reactions between DMAMP and its three isomers were determined at B3LYP/6-311＋＋G（d,p） level of theory. The vibrational spectra were assigned. The A- band resonance Raman spectra were obtained in acetonitrile with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of DMAMP. The B3LYP-TD computation was carried out to determine the relative A-band resonance Raman intensities of the fundamental modes, and the result indicated that the vibronic-coupling existed in Franck-Condon region. Complete active space self-consistent field （CASSCF） calculations were carried out to determine the excitation energies of the lower-lying singlet and triplet excited states, the conical intersection points and the intersystem crossing points. The A-band short-time structural dynamics and the corresponding decay dynamics of DMAMP were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. It was found that a sudden de-conjugation between C1=O6 and C2=C3 occurred at the Franck-Condon region of the S2（ππ^＊） state, while the enhancement of the conjugation interaction between C3 and N（CH3）2, and between C1 and C2 evolutions shortly after the wavepacket leaves away the Pranck-Condon region via the excited state charge redistribution. The de-conjugation interaction between C1=O6 and C2=C3 made the rotation of C3=N（CH3）2 group around the C2-C3 bond much easier, while the enhanced conjugation between C1 and C2, and between C3 and N（CH3）2 made the rotation around the C1-C2 bond and C3-N5 more difficult. It was revealed that the initial structural dynamics of DMAMP was predominantly towards the CI-I（S2/S0） point, while the opportunities towards either CI-2（S2/S0） or CI-3（S2/S0） point were negligible. Two decay channels of DMAMP from S2,FC（ππ^＊） to So or Tl,min via various CIs and ISCs were proposed.
基金the National Key R&D Program of China(Grant No.2018YFA0306303)the National Natural Science Foundation of China(Grant Nos.11834004,61690224,92150105,11904103,12241407,and 12227807)the Science and Technology Commission of Shanghai Municipality(Grant No.21ZR1420100).
文摘Multiphoton resonant excitation and frustrated tunneling ionization,manifesting the photonic and optical nature of the driving light via direct excitation and electron recapture,respectively,are complementary mechanisms to access Rydberg state excitation(RSE)of atoms and molecules in an intense laser field.However,clear identification and manipulation of their individual contributions in the light-induced RSE process remain experimentally challenging.Here,we bridge this gap by exploring the dissociative and nondissociative RSE of H2 molecules using bicircular two-color laser pulses.Depending on the relative field strength and polarization helicity of the two colors,the RSE probability can be boosted by more than one order of magnitude by exploiting the laser waveform-dependent field effect.The role of the photon effect is readily strengthened with increasing relative strength of the second-harmonic field of the two colors regardless of the polarization helicity.As compared to the nondissociative RSE forming H2,the field effect in producing the dissociative RSE channel of eHt;HT is moderately suppressed,which is primarily accessed via a three-step sequential process separated by molecular bond stretching.Our work paves the way toward a comprehensive understanding of the interplay of the underlying field and photon effects in the strong-field RSE process,as well as facilitating the generation of Rydberg states optimized with tailored characteristics.
基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XD30000000)the National Key R&D Program of China(Grant Nos.2018YFA0305802 and 2017YFA0303500)the National Natural Science Foundation of China(Grant No.11774267).Calculations were performed at the supercomputing center of WHU of China.
文摘High-order nonlinear multiphoton absorption is usually inefficient,but can be enhanced by designing resonant excitations between occupied and unoccupied energy levels.We conducted angle-resolved multi-photon photoemission(mPPE)studies on the SnSe_(2)(001)surfaces excited by ultrashort laser pulses.By tuning photon energy and light polarization,we demonstrate the presence of a resonant four-photon photoemission(4PPE)process involving the occupied valence band(VB),the unoccupied second conduction band(CB2)and the unoccupied image-potential state(IPs)of SnSe_(2).In this 4PPE process,VB electrons of SnSe_(2) are resonantly excited into CB2 by adsorbing two photons,followed by the adsorption of another photon to populate the n=1 IPs before being emitted out to the vacuum by adsorbing one more photon.This results in a double-resonant 4PPE process,which exhibits approximately a 40 times enhancement in photoemission yields compared to cases where one of the resonant pathways,CB2→IPs,is inhibited by involving a virtual state instead of the IPs in the 4PPE.The double-resonant 4PPE process efficiently excite the bulk VB electrons outside the vacuum,like taking advantage of resonant“ladders”through two real empty electronic states of SnSe_(2).Our results highlight the important applications of mPPE in probing the band-structure,particularly the unoccupied states,of recently emerging main group dichalcogenide semiconductors.Furthermore,the discovered resonant mPPE process contributes to the exploration of their promising optoelectronic applications.
基金Supported by the National Natural Science Foundation of China(Nos.21273282,21673289,21673288,21173265)the International Cooperation Project Between China and Russia(NSFC-RFBR)(No.21411130185).
文摘The structure and excited state properties of the H- and J-aggregates of the marine carbonyl carotenoid, fucoxanthin(Fx), were studied by various spectroscopic methods, and compared with those of Fx monomers in polar organic solvents. The fluorescent analysis indicated tliat the higher vibronic states of S2 contribute more to populating the S1 state, from which fluorescent emission mainly originates. Resonance Raman and density functional theory calculations confirmed the ‘card-packed' and chead-to-taiF structures of the H- and J-aggregates of Fx, respectively. An fs time-resolved absorption study proved the coexistence of Si and intramolecular charge transfer relaxation pathways upon excitation to the S2 state for both tlie monomers and aggregates.
基金supported by the National Natural Science Foundation of China (Grant No.10574098,10674102)the Natural Science Foundation of Tianjin,China (Grant No.05YFJMJC05200)
文摘The odd-parity high-lying states of the Sm atom are investigated systematically by a three-color resonant excitation scheme with two different excitation paths.The two intermediate states,4f 6 6s7s 7 F 0 and 4f 6 6s7s 7 F 1 are employed for paths I and II,respectively.Fifty-seven bound states are detected with paths I and II in the energy range between 44188 and 45515 cm 1,while 64 autoionizing states are found in the energy range from 45528 to 45761 cm 1.Not only the level energies of all observed states,but also the line widths of autoionizing states are determined.The possible impact of configuration interaction on the line shape of autoionizing states is also discussed.In addition,the total angular momentum is assigned uniquely to most of the states,whereas the information about the relative line intensity of all states is also presented.
基金Supported by the Brazilian funding agencies CNPq-Conselho Nacional de Desenvolvimento Cientifico e Tecnologico and CAPES-Coordenapao de Aperfeicoamento de Pessoal de Nivel Superior。
文摘A rovibrational model,including anharmonic,centrifugal,and Coriolis corrections,is used to calculate π,K,N,and ∑ orbital and radial resonances.The four orbital excitations of the n meson correspond to the/?(1235),ti2(1670),63(2030),and π4(2250)resonances.Its first four radial excitations correspond to the π(1300),π(1800),π(2070),and 7t(2360)resonances.The orbital excitations of the K meson are interpreted as the K_(1)(1270),K_(2)(1770),K_(3)(2320),and K_(4)(2500)resonances;its radial excitations correspond to the K(1460)and K(1830)resonances.The N orbital excitations are identified with the N(1520),N(1680),N(2190),N(2220),and N(2600)resonances.The first four radial excitations of the N family correspond to the N(1440),N(1880),N(2100),and N(2300)resonances.The orbital excitations of the ∑ baryon are associated with the ∑(1670),∑(1915),∑(2100),and ∑(2250)resonances,whereas its radial excitations are identified with the ∑(1660),∑(1770),and ∑(1880)resonances.The proposed rovibrational model calculations show a good agreement with the corresponding experimental values and allow for the prediction of hadron resonances,thereby proving to be useful for the interpretation of excited hadron spectra.
