Resonance Raman study of short-time photodissociation dynamics of the charge-transfer band absorption of nitrobenzene in cyclohexane solution

Resonance Raman spectra were obtained for nitrobenzene in cyclohexane solution with excitation wavelengths in resonance with the charge-transfer (CT) band absorption spectrum. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mainly along the nominal NO2 symmetric stretch mode (nu 11), the nominal benzene ring stretch mode (nu 7), accompanied by a moderate degree of motion along the nominal ONO symmetry bend/benzene ring stretch mode (nu 23), the nominal C-N stretch/benzene ring breathing mode (nu 16), the nominal CCC bending mode (nu 20) and the nominal CCH in-plane bending mode (nu 14). A preliminary resonance Raman intensity analysis was done and the results for nitrobenzene were compared to previously reported results for several nitroalkanes.     

Resonance Raman and density functional theory investigation of the photodissociation dynamics of the A-band absorption of (E)-beta-nitrostyrene in cyclohexane solution

Resonance Raman spectra were obtained for (E)-beta-nitrostyrene in cyclohexane solution with excitation wavelengths in resonance with the charge transfer (CT)-band absorption spectrum. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion predominantly along the nominal NO(2) symmetric stretch mode (nu(14)), the nominal C=C stretch mode (nu(8)), the nominal benzene ring stretch mode (nu(9)), accompanied by a smaller amount of motion along the nominal ONO symmetric bend/benzene ring stretch mode (nu(34)), the nominal CCH in-plane bending mode (nu(20)), the nominal HC=CH in-plane bending mode (nu(18)), the nominal NO(2) asymmetric stretch mode (nu(11)), the nominal C-N stretch/benzene ring breathing mode (nu(27)), and the nominal CCC trigonal bending mode (nu(25)). A preliminary resonance Raman intensity analysis was done and these results for (E)-beta-nitrostyrene were compared to results previously reported for several nitrobenzene and trans-stilbene compounds. The differences and similarities between the CT-band resonance Raman spectra and vibrational reorganizational energies for (E)-beta-nitrostyrene relative to those for nitrobenzene and trans-stilbene were briefly discussed.     

Resonance Raman investigation of the short-time photodissociation dynamics of the charge-transfer absorption of the I2-benzene complex in benzene solution

Resonance Raman spectra were obtained for the I2-benzene complex in benzene solvent with excitation wavelengths in resonance with the CT-band absorption. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mainly along the nominal I-I stretch mode nu(18), the nominal symmetric benzene ring stretch mode nu5, and the nominal symmetric CCH bending nu7. There is also a small contribution from the nominal out-of-plane CH oop wag nu15. A preliminary resonance Raman intensity analysis was done, and the results for the I2-benzene complex were compared to results previously reported for the 1-hexene-I2 complex. We briefly discuss the differences and similarities in the CT-band absorption excitation of an I2-benzene complex relative to those of an I2-alkene complex.     

Resonance Raman intensity analysis of the excited-state proton-transfer dynamics of 2-hydroxybenzaldehyde in the charge-transfer/proton-transfer absorption band

Resonance Raman spectra were obtained for 2-hydroxybenzaldehyde (OHBA) in cyclohexane solution with excitation wavelengths in resonance with the first charge-transfer/proton-transfer (CT/PT) band absorption. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion predominantly along the nominal C=CH in-plane bend+ring deformation modes (nu9, nu10, nu14, nu16, nu18, nu19, nu20, nu26, nu30, nu31, and nu35) accompanied by a smaller amount of motion along the nominal C=O stretch mode (nu7), the nominal C=C-C(=O) in-plane bend modes (nu33 and nu37), and the nominal ring C-O-H in-plane bend modes (nu9 and nu14). A preliminary resonance Raman intensity analysis was done, and these results for the OHBA molecule were compared to results previously reported for the 2-hydroxyacetophenone (OHAP) molecule. Several proton-transfer tautomers in the ground and excited states were predicted from the results of B3LYP/cc-PVTZ, UB3LYP/cc-PVTZ, and CASSCF/cc-PVDZ level of theory computations. The differences and similarities between the CT/PT band resonance Raman spectra and the vibrational reorganizational energies for the OHBA molecule relative to those for the OHAP molecule are briefly discussed.     

2-乙酰基-1-甲基吡咯激发态结构动力学及溶剂效应的共振拉曼光谱和密度泛函理论计算

获取了覆盖紫外光谱中A带和B带吸收的共7个不同激发波长的共振拉曼光谱, 并结合密度泛函理论方法研究了2-乙酰基-1-甲基吡咯(2-Ac-NMP)的A带和B带电子激发和Franck-Condon区域结构动力学. 在TD-B3LYP/6-311++G(d,p)计算水平上, A带和B带吸收的跃迁主体为π→π^* . A带和B带共振拉曼光谱分别指认为13个振动模式和8个振动模式的基频、泛频和组合频, 其中C＝O伸缩振动(ν₈)、C3-C4-C5不对称伸缩振动+C2-C6伸缩振动(ν₁₄)及环上CH面内摇摆(ν₁₈)对拉曼光谱强度贡献最大, 表明2-Ac-NMP的S_π激发态结构动力学主要沿反应坐标展开. 考察了溶剂对共振拉曼光谱强度模式的影响, 结果表明, 在同一溶剂中, 随激发波长由长变短, C＝O伸缩振动模(ν₈)的强度呈现出由强变弱再变强的现象. 这种变化规律与Franck-Condon区域S_n/S_π态混合或势能面交叉相关, 并受溶剂的有效调控.     

Resonance Raman intensity analysis of the excited state proton transfer dynamics of 2-nitrophenol in the charge-transfer band absorption

Resonance Raman spectra were obtained for 2-nitrophenol in cyclohexane solution with excitation wavelengths in resonance with the charge-transfer (CT) proton transfer band absorption. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion along more than 15 normal modes: the nominal CCH bend+CC stretch nu(12) (1326 cm(-1)), the nominal CCC bend nu(23) (564 cm(-1)), the nominal CO stretch+NO stretch+CC stretch nu(14) (1250 cm(-1)), the nominal CCH bend+CC stretch+COH bend nu(15) (1190 cm(-1)); the nominal CCH bend+CC stretch nu(17) (1134 cm(-1)), the nominal CCC bend+CC stretch nu(22) (669 cm(-1)), the nominal CCN bend nu(27) (290 cm(-1)), the nominal NO(2) bend+CC stretch nu(21) (820 cm(-1)), the nominal CCO bend+CNO bend nu(25) (428 cm(-1)), the nominal CC stretch nu(7) (1590 cm(-1)), the nominal NO stretch nu(8) (1538 cm(-1)), the nominal CCC bend+NO(2) bend nu(20) (870 cm(-1)), the nominal CC stretch nu(6) (1617 cm(-1)), the nominal COH bend+CC stretch nu(11) (1382 cm(-1)), nominal CCH bend+CC stretch nu(9) (1472 cm(-1)). A preliminary resonance Raman intensity analysis was done and the results for 2-nitrophenol were compared to previously reported results for nitrobenzene, p-nitroaniline, and 2-hydroxyacetophenone. The authors briefly discuss the differences and similarities in the CT-band absorption excitation of 2-nitrophenol relative to those of nitrobenzene, p-nitroaniline, and 2-hydroxyacetophenone.     

Resonance Raman study of the A-band short-time photodissociation dynamics of 2-iodothiophene

Resonance Raman spectra were obtained for 2-iodothiophene in cyclohexane solution with excitation wavelengths in resonance with the A-band absorption spectrum. These resonance Raman spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mainly along the nominal symmetric C=C stretch of the thienyl ring and accompanied by a moderate amount of motion along the nominal symmetric CSC stretch, the nominal antisymmetric CSC stretch, and the nominal C-I stretch vibrational modes. A preliminary resonance Raman intensity analysis was done for the A-band resonance Raman spectra of 2-iodothiophene. These results were compared to previous results for related iodobenzene and iodoalkane molecules that also contain a C-I chromophore and the similarities and differences in the short-time photodissociation dynamics were discussed.     

A resonance Raman spectroscopic and CASSCF investigation of the Franck-Condon region structural dynamics and conical intersections of thiophene

Resonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ～240?nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the C-S antisymmetry stretch +C-C=C bend mode ν(21)(B(2)) at 754?cm(-1) and the H(7)C(3)-C(4)H(8) twist ν(9)(A(2)) at 906?cm(-1), suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points (1)B(1)/(1)A(1) and (1)B(2)/(1)A(1) between 2?(1)A(1) and 1?(1)B(2) or 1?(1)B(1) potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C-S bonds and via the conical intersection point (1)B(1)/(1)A(1) was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point (1)B(2)/(1)A(1) was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface.     

N-甲基吡咯-2-甲醛激发态结构动力学及其溶剂效应的共振拉曼光谱和密度泛函理论研究

获取了覆盖N-甲基吡咯-2-甲醛(NMPCA)A-带和B-带电子吸收共7个激发波长的共振拉曼光谱,并结合含时密度泛函理论(TD-DFT)方法研究了的A-带和B-带电子激发和Franck-Condon区域结构动力学.TD-B3LYP/6-311++G(d,p)计算表明:A-带和B-带电子吸收的跃迁主体为π→π*.共振拉曼光谱可以指认为,11-13振动模式(A-带激发)或者7-11振动模式(B-带激发)的基频、倍频和组合频,其中C=O伸缩振动(ν7)、环的变形振动+N1-C6伸缩振动(ν17)、环的变形振动(ν21)和C6-N1-C2/C2-C3-C4不对称伸缩振动(ν14)占据了绝大部分.这表明NMPCA的Sπ激发态结构动力学主要沿C=O伸缩振动、环的变形振动和环上N1-C6伸缩振动等反应坐标展开.在同一溶剂的共振拉曼光谱中随激发波长由长变短,ν7与ν14的强度比呈现出由强变弱再变强的现象,这种变化规律被认为与Franck-Condon区域Sn/Sπ态混合或势能面交叉有关.溶剂对Sn/Sπ态混合或势能面交叉具有调控作用.     

6-N,N-二甲基腺嘌呤激发态结构动力学的共振拉曼光谱

采用共振拉曼光谱技术和密度泛函理论方法研究了6-N,N-二甲基腺嘌呤(DMA)的A带和B带电子激发和Franck-Condon 区域结构动力学. π_H→π_L^*跃迁是A带吸收的主体, 其振子强度约占整个A带吸收的79%.由弥散轨道参与的n→Ryd 和π_H→Ryd 跃迁在B带跃迁中扮演重要角色, 其振子强度约占B带吸收的62%,而在A带吸收中占主导的π_H→π_L^*跃迁的振子强度在B带吸收中仅占33%. 嘌呤环变形伸缩+C8H/N9H面内弯曲振动ν₂₃和五元环变形伸缩+C8H弯曲振动ν₁₃的基频、泛频和合频占据了A带共振拉曼光谱强度的绝大部分, 说明¹π_Hπ_L^*激发态结构动力学主要沿嘌呤环的变形伸缩振动, N9H/C8H/C2H弯曲振动等反应坐标展开, 而ν₁₀, ν₂₉, ν₂₁, ν₂₆和ν₄₀的基频、泛频和合频占据了B带共振拉曼光谱强度的主体部分, 它们决定了B带激发态的结构动力学. A带共振拉曼光谱中ν₂₆和ν₁₂被认为与1nπ*/1ππ*势能面锥型交叉有关. B带共振拉曼光谱中ν₂₁的激活与¹ππ^*/¹πσ_N9H^*势能面锥型交叉相关.     

Resonance Raman spectroscopy and density functional theory calculation study of photodecay dynamics of tetra(4-carboxyphenyl) porphyrin

The 397.9 nm, 416.0 nm and 435.7 nm resonance Raman spectra were acquired for meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP) in tetrahydrofuran solution, and the Raman effect of relaxation dynamics was analyzed according to Herzberg-Teller (vibronic coupling) contributions. Density functional calculations were done to help the elucidation of the Soret (B(x) and B(y)-band) electronic transitions and the corresponding photo relaxation dynamics of TCPP. The spectra indicate that the Franck-Condon region photo relaxation dynamics upon S(0) → S(4) electronic transition are predominantly along the totally symmetric C(m)-ph stretch and Porphin ring breath stretch, and simultaneously along the asymmetric ν(C(m)-Phenyl) + δ(N-H) and ν(C(α)-C(m)-C(α))(as) + def (pyr) vibrational relaxation processes. The excited state structural dynamics of TCPP determined from the resonance Raman spectra show that the internal conversion between the B(y) and B(x) electronic states occurs in tens of femtoseconds, and the electronic relaxation dynamics were firstly interpreted taking into account the time-dependent wave packet theory and Herzberg-Teller (vibronic coupling) contributions.     

Photodecay dynamics of octaethylporphine in the condensed phase explored via resonance Raman spectroscopy and density functional theory calculation

Resonance Raman spectra of free-base octaethylporphine (OEP) were obtained with 368.9 nm, 397.9 nm and 416.0 nm excitation wavelengths, and density functional calculations were done to help the elucidation of Soret (B(x) and B(y)-band) electronic transitions and the corresponding photo relaxation dynamics of OEP. The RRs indicate that the Franck-Condon region photo relaxation dynamics upon S(0)→S(8) electronic transition is predominantly along the totally symmetric C(m)C(α) stretch, the C(β)C(β) stretch, and simultaneously along the asymmetric δ(pyr deformation),γ(CH(2)) vibrational relaxation processes. The excited state structural dynamics of OEP determined from resonance Raman spectra show that the internal conversion between B(y) and B(x) electronic states occurs in tens of femtoseconds and the electronic relaxation dynamics were firstly interpreted with account of the time-dependent wave packet theory and Herzberg-Teller (vibronic coupling) contributions.     

尿嘧啶和5-氯尿嘧啶1S0→1S2跃迁动态结构的共振拉曼光谱

采用含时量子波包理论的简单模型对5-氯尿嘧啶和尿嘧啶的共振拉曼光谱开展了强度分析拟合, 获得了1(π, π*)激发态的几何结构变化动态特征. 结果表明, 尿嘧啶1S0→1S2跃迁的动态结构特征因5-位氯原子取代而改变. 5-氯尿嘧啶的动态结构特征主要沿C5=C6伸缩振动+C6H12 弯曲振动和N3H9/N1H7弯曲振动+N1C6伸缩振动反应坐标展开, 而尿嘧啶的动态结构特征主要沿嘧啶环的伸缩振动+C5H11/C6H12/N1H7弯曲振动和C4=O10伸缩振动反应坐标展开. π和π*轨道中氯原子的pz电子参与嘧啶环的p-π共轭作用导致了在1(π, π*)激发态上5-氯尿嘧啶的振动重组能更多地配分给嘧啶环的弯曲振动模式和C5=C6伸缩振动模式. 尿嘧啶在甲醇中的激发态动态结构特征与在水中的基本一致, 但波包沿C5H11/C6H12/N1H7弯曲振动+N1C6伸缩振动(υ12)和环呼吸振动(υ17)反应坐标的运动明显增强.     

Structure and dynamics of the solvated electron in alcohols from resonance Raman spectroscopy

Resonance Raman (RR) spectroscopy is used to probe the structure and excited-state dynamics of the solvated electron in the primary liquid alcohols methanol (MeOH), ethanol (EtOH), n-propanol (n-PrOH), and n-butanol (n-BuOH). The strong resonance enhancements (>or=10(4) relative to pure solvent) of the libration, CO stretch, COH bend, CH3 bend, CH2 bend, and OH stretch reveal significant Franck-Condon coupling of the intermolecular and intramolecular vibrational modes of the solvent to the electronic excitation of the solvated electron. All enhanced bands are fully accounted for by a model of the solvated electron that is comprised of several nearby solvent molecules that are only perturbed by the presence of the electron; no new molecular species are required to explain our data. The 340 cm(-1) downshift observed for the OH stretch frequency of e-(MeOH), relative to pure solvent, strongly suggests that the methanol molecules in the first solvent shell have the hydroxyl group directed linearly toward the excess electron density. The smaller downshifts observed for e-(EtOH), e-(n-PrOH), and e-(n-BuOH) are explained in terms of a OH group that is bent 28-40 degrees from linear. The Raman cross sections and absorption spectra are modeled, lending quantitative support for the inhomogeneous origin of the broad absorption spectra, the necessity of OH local motion in all enhanced Raman modes of the alcohols, and the dominant librational response of the solvent upon photoexcitation of the electron.     

Resonance Raman Spectroscopic and Theoretical Study of Geometry Distortion of Thiourea in 21A State

The A-band resonance Raman spectra of thiourea were obtained in water and acetonitrile so-lution. 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 re-sults indicate that largest change in the displacement takes place with the C=S stretch mode ν₆ (|△|=0.95) and noticeable changes appear in the H₅N₃H₆+H₈N₄H₇ wag ν₅ (|△|=0.19), NCN symmetric stretch+C=S stretch+N₃H₆+H₈N₄ wag ν₄ (|△|=0.18), while the moderate intensities of 2ν₁₅ and 4ν₁₅ are mostly due to the large excited state frequency changes of ν₁₅, 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.     

3-二甲氨基-2-甲基丙烯醛S2激发态结构动力学

采用共振拉曼光谱和完全活性自洽场理论计算研究了3-二甲氨基-2-甲基丙烯醛（DMAMP）光激发到S2（ππ^＊）态后的光物理性能,在B3LYP／6—311＋＋G（d,p）水平计算确定了DMAMP与其三种异构体之间的基态异构化能垒,指认了振动光谱．采用涵盖紫外强吸收带的激光波长,获得了DMAMP在环己烷、乙腈和甲醇溶剂中的A-带共振拉曼光谱,含时密度泛函方法计算确定了该光谱中基频的相对强度,发现振动-电子耦合发生在S2（）态的Franck—Condon区域．CASSCF计算方法确定低单重和三重激发态、势能面锥形交叉点和系间窜跃点的激发能．共振拉曼光谱强度模式分析和CASSCF计算获得了DMAMP的A一带短时结构动力学和其后的衰变动力学表明,C1=06和C2=C3之间的瞬时去共轭效应发生在S2（ππ^＊）态的Franck—Condon区域,激发态电荷重分布机制表明,C3和二甲氨基之间以及C1和C2之间的共轭增强效应发生在波包离开Franck-Condon区域后．C1=06和C2=C3之间的去共轭效应使得-C3=N（CH3）2沿着C2-C3键旋转更加容易,C1-C2之间以及C3和N（CH3）的共轭增强效应使得绕C1-C2和C3-N5旋转变得比较困难．这些表明DMAMP初始结构动力学沿着CI-1（S2／S0）交叉点展开,而沿CI-2（S2／S0）和[CI-3（S2／S0）交叉点展开的几率可以忽略,提出了DMAMP分子受光激发从S2,FC（ππ^＊）经由各锥形交叉点和各系间窜跃点回到S0或T1,min的两个衰变通道。     

Electronic and vibrational spectroscopy and vibrationally mediated photodissociation of V+(OCO)

Electronic spectra of gas-phase V+(OCO) are measured in the near-infrared from 6050 to 7420 cm(-1) and in the visible from 15,500 to 16,560 cm(-1), using photofragment spectroscopy. The near-IR band is complex, with a 107 cm(-1) progression in the metal-ligand stretch. The visible band shows clearly resolved vibrational progressions in the metal-ligand stretch and rock, and in the OCO bend, as observed by Brucat and co-workers. A vibrational hot band gives the metal-ligand stretch frequency in the ground electronic state nu3' = 210 cm(-1). The OCO antisymmetric stretch frequency in the ground electronic state (nu1') is measured by using vibrationally mediated photodissociation. An IR laser vibrationally excites ions to nu1' = 1. Vibrationally excited ions selectively dissociate following absorption of a second, visible photon at the nu1' = 1 <-- nu1' = 1 transition. Rotational structure in the resulting vibrational action spectrum confirms that V+(OCO) is linear and gives nu1' = 2392.0 cm(-1). The OCO antisymmetric stretch frequency in the excited electronic state is nu1' = 2368 cm(-1). Both show a blue shift from the value in free CO2, due to interaction with the metal. Larger blue shifts observed for complexes with fewer ligands agree with trends seen for larger V+(OCO)n clusters.     

Reaction dynamics and vibrational spectroscopy of CH3D molecules with both C-H and C-D stretches excited

State-resolved reactions of CH3D molecules containing both C-H and C-D stretching excitation with Cl atoms provide new vibrational spectroscopy and probe the consumption and disposal of vibrational energy in the reactions. The vibrational action spectra have three different components, the combination of the C-H symmetric stretch and the C-D stretch (nu1 + nu2), the combination of the C-D stretch and the C-H antisymmetric stretch (nu2 + nu4), and the combination of the C-D stretch and the first overtone of the CH3 bend (nu2 + 2nu5). The simulation for the previously unanalyzed (nu2 + nu4) state yields a band center of nu0 = 5215.3 cm(-1), rotational constants of A = 5.223 cm(-1) and B = 3.803 cm(-1), and a Coriolis coupling constant of zeta = 0.084. The reaction dynamics largely follow a spectator picture in which the surviving bond retains its initial vibrational excitation. In at least 80% of the reactive encounters of vibrationally excited CH3D with Cl, cleavage of the C-H bond produces CH2D radicals with an excited C-D stretch, and cleavage of the C-D bond produces CH3 radicals with an excited C-H stretch. Deviations from the spectator picture seem to reflect mixing in the initially prepared eigenstates and, possibly, collisional coupling during the reaction.     

Gas and solution phase chloroiodomethane short-time photodissociation dynamics in the B-band absorption

Resonance Raman spectra were obtained within and to the red of the B-band absorption spectrum of gas phase chloroiodomethane and chloroiodomethane in cyclohexane solvent. The spectra show the fundamental and overtones of the nominal C---I stretch (nν₅) and combination bands of the CH₂ wag (ν₃), I---C---Cl bend (ν₆), and the CH₂ scissor (ν₂) fundamentals with the C---I stretch bands (nν₅). The chloroiodomethane B-band short-time photodissociation dynamics have significant substituent effects relative to the B-band of iodomethane due to the presence of the C---Cl chromophore n(X) → σ^* (C---X) transitions ≈170 nm that are close to the B-band absorption of chloroiodomethane but absent in iodomethane.     

Ultraviolet photodissociation dynamics of the SH radical

Ultraviolet (UV) photodissociation dynamics of jet-cooled SH radical (in X 2pi(3/2), nu"=0-2) is studied in the photolysis wavelength region of 216-232 nm using high-n Rydberg atom time-of-flight technique. In this wavelength region, anisotropy beta parameter of the H-atom product is approximately -1, and spin-orbit branching fractions of the S(3P(J)) product are close to S(3P2):S(3P1):S(3P0)=0.51:0.36:0.13. The UV photolysis of SH is via a direct dissociation and is initiated on the repulsive 2sigma- potential-energy curve in the Franck-Condon region after the perpendicular transition 2sigma(-)-X 2pi. The S(3P(J)) product fine-structure state distribution approaches that in the sudden limit dissociation on the single repulsive 2sigma- state, but it is also affected by the nonadiabatic couplings among the repulsive 4sigma-, 2sigma-, and 4pi states, which redistribute the photodissociation flux from the initially excited 2sigma- state to the 4sigma- and 4pi states. The bond dissociation energy D0(S-H)=29,245+/-25 cm(-1) is obtained.