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1.
Rotationally resolved fluorescence excitation spectra of the 0(0)(0) bands of the S1<--S0 electronic transitions of 2- and 5-methylpyrimidine (2MP and 5MP, respectively) have been observed and assigned. Both spectra were found to contain two sets of rotational lines, one associated with the sigma=0 torsional level and the other associated with the sigma=+/-1 torsional level of the attached methyl group. Analyses of their structure using the appropriate torsion-rotation Hamiltonian yields the methyl group torsional barriers of V6'=1.56 and V6'=8.28 cm(-1) in 2MP and V6'=4.11 and V6'=58.88 cm(-1) in 5MP. Many of the lines in both spectra are fragmented by couplings with lower lying triplet states. Analyses of some of these perturbations yield approximate values of the intersystem crossing matrix elements, from which it is concluded that the sigma=+/-1 torsional levels of the S1 state are significantly more strongly coupled to the T1 state than the sigma=0 torsional levels.  相似文献   

2.
We report the analysis of the S1<--S0 rotational band contours of jet-cooled 5-methyl-2-hydroxypyrimidine (5M2HP), the enol form of deoxythymine. Unlike thymine, which exhibits a structureless spectrum, the vibronic spectrum of 5M2HP is well structured, allowing us to determine the rotational constants and the methyl group torsional barriers in the S0 and S1 states. The 0(0)(0), 6a(0)(1), 6b(0)(1), and 14(0)(1) band contours were measured at 900 MHz (0.03 cm(-1)) resolution using mass-specific two-color resonant two-photon ionization (2C-R2PI) spectroscopy. All four bands are polarized perpendicular to the pyrimidine plane (>90% c type), identifying the S1<--S0 excitation of 5M2HP as a 1nπ* transition. All contours exhibit two methyl rotor subbands that arise from the lowest 5-methyl torsional states 0A" and 1E". The S0 and S1 state torsional barriers were extracted from fits to the torsional subbands. The 3-fold barriers are V3" = 13 cm(-1) and V3' = 51 cm(-1); the 6-fold barrier contributions V6" and V6' are in the range of 2-3 cm(-1) and are positive in both states. The changes of A, B, and C rotational constants upon S1 <--S0 excitation were extracted from the contours and reflect an “anti-quinoidal” distortion. The 0(0)(0) contour can only be simulated if a 3 GHz Lorentzian line shape is included, which implies that the S1(1nπ*) lifetime is ~55 ps. For the 6a(0)(1) and 6b(0)(1) bands, the Lorentzian component increases to 5.5 GHz, reflecting a lifetime decrease to ~30 ps. The short lifetimes are consistent with the absence of fluorescence from the 1nπ* state. Combining these measurements with the previous observation of efficient intersystem crossing (ISC) from the S1 state to a long-lived T1 (3nπ*) state that lies ~2200 cm(-1) below [S. Lobsiger, S. et al. Phys. Chem. Chem. Phys. 2010, 12, 5032] implies that the broadening arises from fast intersystem crossing with k(ISC) ≈ 2 × 10(10) s(-1). In comparison to 5-methylpyrimidine, the ISC rate is enhanced by at least 10 000 by the additional hydroxy group in position 2.  相似文献   

3.
Rotationally resolved fluorescence excitation spectra of several torsional bands in the S1 <-- S0 electronic spectra of 2-methylanisole (2MA) and 3-methylanisole (3MA) have been recorded in the collision-free environment of a molecular beam. Some of the bands can be fit with rigid rotor Hamiltonians; others exhibit perturbations produced by the coupling between the internal rotation of the methyl group and the overall rotation of the entire molecule. Analyses of these data show that 2MA and 3MA both have planar heavy-atom structures; 2MA has trans-disposed methyl and methoxy groups, whereas 3MA has both cis- and trans-disposed substituents. The preferred orientations (staggered or eclipsed) in two of the conformers and the internal rotation barriers of the methyl groups in all three conformers change when they are excited by light. Additionally, the values of the barriers opposing their motion depend on the relative positions of the substituent groups, in both electronic states. In contrast, no torsional motions of the attached methoxy groups were detected. Possible reasons for these behaviors are discussed.  相似文献   

4.
Rotationally resolved electronic spectra of several low frequency vibrational bands that appear in the S(1) ← S(0) transition of 4-fluorobenzyl alcohol (4FBA) in the collision-free environment of a molecular beam have been observed and assigned. Each transition is split into two or more components by the tunneling motion of the attached -CH(2)OH group. A similar splitting is observed in the microwave spectrum of 4FBA. Analyses of these data show that 4FBA has a gauche structure in both electronic states, but that the ground state C(1)C(2)-C(7)O dihedral angle of ~60° changes by ~30° when the photon is absorbed. The barriers to the torsional motion of the attached -CH(2)OH group are also quite different in the two electronic states; V(2) ~ 300 cm(-1) high and ~60° wide in the S(0) state, and V(2) ~ 300 cm(-1) high and ~120° wide (or V(2) ~ 1200 cm(-1) high and ~60° wide) in the S(1) state. Possible reasons for these behaviors are discussed.  相似文献   

5.
We investigated the spectroscopy of the first excited singlet electronic state S1 of 2-phenylindene using both fluorescence excitation spectroscopy and resonantly enhanced multiphoton ionization spectroscopy. Moreover, we investigated the dynamics of the S1 state by determining state-selective fluorescence lifetimes up to an excess energy of approximately 3400 cm(-1). Ab initio calculations were performed on the torsional potential energy curve and the equilibrium and transition state geometries and normal-mode frequencies of the first excited singlet state S1 on the CIS level of theory. Numerous vibronic transitions were assigned, especially those involving the torsional normal mode. The torsional potentials of the ground and first excited electronic states were simulated by matching the observed and calculated torsional frequency spacings in a least-squares fitting procedure. The simulated S1 potential showed very good agreement with the ab initio potential calculated on the CIS/6-31G(d,p) level of theory. TDDFT energy corrections improved the match with the simulated S(1) torsional potential. The latter calculation yielded a torsional barrier of V2 = 6708 cm(-1), and the simulation a barrier of V2 = 6245 cm(-1). Ground-state normal-mode frequencies were calculated on the B3LYP/6-31G(d,p) level of theory, which were used to interpret the infrared spectrum, the FDS spectrum of the transition and hot bands of the FES spectrum. The fluorescence intensities of the nu49 overtone progression could reasonably be reproduced by considering the geometry changes upon electronic excitation predicted by the ab initio calculations. On the basis of the torsional potential calculations, it could be ruled out that the uniform excess energy dependence of the fluorescence lifetimes is linked to the torsional barrier in the excited state. The rotational band contour simulation of the transition yielded rotational constants in close agreement to the ab initio values for both electronic states. Rotational coherence signals were obtained by polarization-analyzed, time-resolved measurements of the fluorescence decay of the transition. The simulation of these signals yielded corroborating evidence as to the quality of the ab initio calculated rotational constants of both states. The origin of the anomalous intensity discrepancy between the fluorescence excitation spectrum and the REMPI spectrum is discussed.  相似文献   

6.
In electron donor/acceptor species such as 4-(dimethylamino)benzonitrile (DMABN), the excitation to the S(2) state is followed by internal conversion to the locally excited (LE) state. Dual fluorescence then becomes possible from both the LE and the twisted intramolecular charge-transfer (TICT) states. A detailed mechanism for the ICT of DMABN and 4-aminobenzonitrile (ABN) is presented in this work. The two emitting S(1) species are adiabatically linked along the amino torsion reaction coordinate. However, the S(2)/S(1) CT-LE radiationless decay occurs via an extended conical intersection "seam" that runs almost parallel to this torsional coordinate. At the lowest energy point on this conical intersection seam, the amino group is untwisted; however, the seam is accessible for a large range of torsional angles. Thus, the S(1) LE-TICT equilibration and dual fluorescence will be controlled by (a) the S(1) torsional reaction path and (b) the position along the amino group twist coordinate where the S(2)/S(1) CT-LE radiationless decay occurs. For DMABN, population of LE and TICT can occur because the two species have similar stabilities. However, in ABN, the equilibrium lies in favor of LE, as a TICT state was found at much higher energy with a low reaction barrier toward LE. This explains why dual fluorescence cannot be observed in ABN. The S(1)-->S(0) deactivation channel accessible from the LE state was also studied.  相似文献   

7.
We present a computer program that is capable of fitting n-fold torsional barriers Vn (n = 2-6) and torsional constants F simultaneously to high- and low-resolution spectroscopic data of different isotopomeric internal rotors. The program has been utilized to fit independently barriers and torsional constants for both electronic states of several aromatic clusters. The constant F of the ammonia moiety in the phenol-ammonia cluster is shown to decrease upon electronic excitation, thus imaging the formation of a hydrogen-bonded complex between the phenoxy radical and the NH4 radical in the excited state. In contrast, for the naphthol-ammonia 1:1 clusters no change of F of ammonia could be found. For phenol-methanol cluster we found a decrease of F upon excitation which points to a stronger hydrogen bond between phenol and methanol in the excited state. A strong reduction of the torsional barrier upon excitation points to the formation of a methoxonium radical in a similar photoreaction as in phenol-ammonia cluster. For the phenol-water system we postulate the same mechanism, a photoreaction, which leads to a translocated hydrogen atom in the S1 state what can be deduced from the change of the torsional constant upon electronic excitation.  相似文献   

8.
Rotationally resolved S(1) <-- S(0) electronic spectra of 1,2-dimethoxybenzene (DMB) and its water complex have been observed and assigned. The derived values of the rotational constants show that the bare molecule has a planar heavy-atom structure with trans-disposed methoxy groups in its ground and excited electronic states. The transition of DMB is polarized along the b-axis bisecting the methoxy groups, demonstrating that its S(1) state is an (1)L(b) state. Higher energy bands of DMB are also polarized along the b-axis and have been tentatively assigned to different vibrational modes of the (1)L(b) state. The water complex origin appears 127 cm(-1) to the blue of the bare molecule origin. Analyses of the high resolution spectra of DMB/H(2)O and DMB/D(2)O suggest that the water molecule is attached via two O-H...O hydrogen bonds to the methoxy groups in both electronic states. A tunneling motion of the attached water molecule is revealed by a splitting of these spectra into two subbands. Potential barriers to this motion have been determined.  相似文献   

9.
Two new red-degraded bands in the room-temperature vacuum-ultraviolet absorption spectrum of carbon monoxide have been identified in the 94,000-94,500 cm(-1) energy region and analyzed. One of the bands at approximately 94,225 cm(-1) (106.1 nm) has three observable bandheads and is partially overlapped with the strong C 1Sigma+-X 1Sigma+ (1-0) transition at lower energy. It is assigned to the c 3Pi-X 1Sigma+ (1-0) transition. The other band at approximately 94,437 cm(-1) (105.9 nm) with one clear bandhead is assigned to the k 3Pi-X 1Sigma+ (5-0) transition. A strong homogeneous perturbation was found to exist between the two upper states that strongly influences the line positions and shapes of these bands. A rotational deperturbation analysis was performed and molecular rotational constants for both upper states were determined. These deperturbed molecular constants are entirely consistent with the expected values for the k 3Pi valence and c 3Pi Rydberg states. The Hamiltonian interaction term between these two states is found to be separable into vibrational and electronic factors and the electronic factor is determined to be H(e)=323+/-40 cm(-1). A discrepancy in the literature regarding the location of the c 3Pi (v=1) state is identified and discussed.  相似文献   

10.
Rotationally resolved fluorescence excitation spectra of several bands in the S1<--S0 electronic spectrum of 9,10-dihydrophenanthrene (DHPH) have been observed and assigned. Each band was fit using rigid rotor Hamiltonians in both electronic states. Analyses of these data reveal that DHPH has a nonplanar configuration in its S0 state with a dihedral angle between the aromatic rings (phi) of approximately 21.5 degrees. The data also show that excitation of DHPH with UV light results in a more planar structure of the molecule in the electronically excited state, with phi approximately 8.5 degrees. Three prominent Franck-Condon progressions appear in the low resolution spectrum, all with fundamental frequencies lying below 300 cm(-1). Estimates of the potential energy surfaces along each of these coordinates have been obtained from analyses of the high resolution spectra. The remaining barrier to planarity in the S1 state is estimated to be approximately 2650 cm(-1) along the bridge deformation mode and is substantially reduced by excitation of the molecule along the (orthogonal) ring twisting coordinate.  相似文献   

11.
Ab initio calculations have been performed to examine the photochemical behavior of 4-(dimethylamino)benzenzonitrile (DMABN). The conical intersection between S2 and S1 (S2/S1-CIX), where the internal conversion takes place after the main transition of S0-S2 at the equilibrium geometry in S0, is characterized by a dimethylamino-twisted quinoid structure where aromaticity of the benzene ring is lost. The optimized geometry of the charge transfer (CT) state in S1 has a feature similar to that of S2/S1-CIX but is not energetically stabilized so much. Consequently, electronically excited DMABN with CT character relaxes into the most stable locally excited (LE) state in S1 through a recrossing at S2/S1-CIX in gas phase or nonpolar solvent. In polar solvent, in contrast, the equilibration between LE and CT takes place in S1 so that the CT state is more stable because of electrostatic interaction. The excited states of DMABN derivatives have been also examined. On the basis of the present computational results, a new and simple guiding principle of the emission properties is proposed, where conventional twisted intramolecular CT (TICT) and planar intramolecular CT (PICT) models are properly incorporated.  相似文献   

12.
The UV fluorescence excitation and dispersed fluorescence spectra of a jet-cooled o-methylaniline have been obtained for the S1 <-- S0 transition, in which some of the bands have been observed and assigned for the first time. The origin of the electronic transition appears at 34,328.4 cm(-1). It was found that the spectra exhibit an important feature corresponding to the internal rotation of the methyl group in the electronic ground and excited states. Ab initio calculations at MP2/6-31 + G* and CIS/6-31 + G* show that the optimised structure of o-methylaniline in the ground state is not planar with the amino group having sp3 hybridation-like character due to the existence of lone paired electrons on the N atom. Upon electronic excitation, the C-N bond exhibits a partial double character, as in the case of other aniline derivatives.  相似文献   

13.
The laser induced fluorescence excitation and dispersed fluorescence spectra of three nitrogen heterocyclic molecules 1-methyl-2(1H)pyridone (1MPY), 1-methyl-2(1H)pyridinimine (1MPI), and 3-methyl-2(1H)pyridone (3MPY) have been studied under supersonic jet cooled condition. The methyl torsional and some low frequency vibrational transitions in the fluorescence excitation spectrum were assigned for 1MPY. These new assignments modify the potential parameters to the methyl torsion reported earlier. Some striking similarities exist between the torsional and vibrational transitions in the fluorescence excitation spectra of 1MPY and 1MPI. Apart from pure torsional transitions, a progression of vibration-torsion combination bands was observed for both these molecules. The excitation spectrum of 3MPY resembles the spectrum of its parent molecule, 2-pyridone. The barrier height of the methyl torsion in the excited state of 3MPY is highest amongst all these molecules, whereas the barrier in 1MPI is higher than that of 1MPY. To get an insight into the methyl torsional barrier for these molecules, results of the ab initio calculations were compared with the experimental results. It was found that the conformation of the methyl group undergoes a 60 degrees rotation in the excited state in all these molecules with respect to their ground state conformation. This phase shift of the excited state potential is attributed to the pi*-sigma* hyperconjugation between the out-of-plane hydrogen of the methyl group and the molecular frame. It has been inferred that the change in lowest unoccupied molecular orbital energy plays the dominant role in the excited state barrier formation.  相似文献   

14.
The kinetics of the intramolecular charge-transfer (ICT) reaction of 4-(dimethylamino)benzonitrile (DMABN) in the polar solvent acetonitrile (MeCN) is investigated by fluorescence quantum yield and picosecond time-correlated single photon counting (SPC) experiments over the temperature range from -45 to +75 degrees C, together with femtosecond Sn <-- S1 transient absorption measurements at room temperature. For DMABN in MeCN, the fluorescence from the locally excited (LE) state is strongly quenched, with an unquenched to quenched fluorescence quantum yield ratio of 290 at 25 degrees C. Under these conditions, even very small amounts of the photoproduct 4-(methylamino)benzonitrile (MABN) severely interfere, as the LE fluorescence of MABN is in the same spectral range as that of DMABN. The influence of photoproduct formation could be overcome by a simultaneous analysis of the picosecond and photostationary measurements, resulting in data for the activation barriers Ea (5 kJ/mol) and Ed (32 kJ/mol) of the forward and backward ICT reaction as well as the ICT reaction enthalpy and entropy: DeltaH (-27 kJ/mol) and DeltaS [-38 J/(mol K)]. The reaction hence takes place over a barrier, with double-exponential fluorescence decays, as to be expected in a two-state reaction. From femtosecond transient absorption down to 200 fs, the LE and ICT excited state absorption (ESA) spectra of DMABN in n-hexane (LE) and in MeCN (LE and ICT) and also of 4-aminobenzonitrile in MeCN (LE) are obtained. For DMABN in MeCN, the quenching of the LE and the rise of the ICT ESA bands occurs with a single characteristic time of 4.1 ps, the same as the ICT reaction time found from the picosecond SPC experiments at 25 degrees C. The sharp ICT peak at 320 nm does not change its spectral position after a pump-probe delay time of 200 fs, which suggests that large amplitude motions do not take place after this time. The increase with time in signal intensity observed for the LE spectrum of DMABN in n-hexane between 730 and 770 nm, is attributed to solvent cooling of the excess excitation energy and not to an inverse ICT --> LE reaction, as reported in the literature.  相似文献   

15.
The laser induced fluorescence excitation and single vibronic excitation dispersed fluorescence spectra have been studied for supersonic jet cooled 1-methyl-2(1h)-pyridone. The methyl torsional bands and some low frequency vibrational transitions were assigned for both ground and excited states. The torsional parameters V(3)=244 cm(-1) and V(6)=15 cm(-1) for the ground state and V(3)=164 cm(-1) and V(6)=40 cm(-1) for the excited state were obtained. To get the insight into the methyl torsional barrier, ab initio calculations were performed and compared with the experimental results. Origin of potential barrier was traced by partitioning the barrier energy into changes in bond-antibond interaction, structural, and steric energies accompanying methyl rotation using natural bond orbital analysis. The role of local interactions in ascertaining the barrier potential reveals that its nature cannot be understood without considering the molecular flexing. The hyperconjugation between CHsigma(*) and ring pi(*) observed in lowest unoccupied molecular orbital (LUMO) stabilizes the methyl group conformer that undergoes a 60 degrees rotation in the excited state with respect to that of the ground state, and it is the change in LUMO that plays important role in the excited state barrier formation.  相似文献   

16.
The intramolecular charge transfer (ICT) reaction of 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6) in n-hexane and acetonitrile (MeCN) is investigated by picosecond fluorescence experiments as a function of temperature and by femtosecond transient absorption measurements at room temperature. NTC6 in n-hexane is dual fluorescent from a locally excited (LE) and an ICT state, with a quantum yield ratio Phi'(ICT)/Phi(LE) of 0.35 at +25 degrees C and 0.67 at -95 degrees C, whereas in MeCN mainly an ICT emission is observed. From the temperature dependence of Phi'(ICT)/Phi(LE) for NTC6 in n-hexane, an LE/ICT enthalpy difference DeltaH of -2.4 kJ/mol is determined. For comparison, 1-isopropyl-6-cyano-1,2,3,4-tetrahydroquinoline (NIC6) is also investigated. This molecule does not undergo an ICT reaction, because of its larger energy gap DeltaE(S1,S2). From the molar absorption coefficient epsilonmax of NTC6 as compared with other aminobenzonitriles, a ground-state amino twist angle theta of approximately 22 degrees is deduced. The increase of epsilonmax between n-hexane and MeCN indicates that theta decreases when the solvent polarity becomes larger. Whereas single-exponential LE fluorescence decays are obtained for NIC6 in n-hexane and MeCN, the LE and ICT decays of NTC6 in these solvents are double exponential. For NTC6 in n-hexane at -95 degrees C, with a shortest decay time of 20 ps, the forward (ka=2.5x10(10) s(-1)) and backward (kd=2.7x10(10) s(-1)) rate constants for the LE<-->ICT reaction are determined from the time-resolved LE and ICT fluorescence spectra. For NTC6 in n-hexane and MeCN, the excited-state absorption (ESA) spectrum at 200 fs after excitation is similar to the LE(ESA) spectra of NIC6 and 4-(dimethylamino)benzonitrile (DMABN), showing that LE is the initially excited state for NTC6. These results indicate that the LE states of NTC6, NIC6, and DMABN have a comparable molecular structure. The ICT(ESA) spectrum of NTC6 in n-hexane and MeCN resembles that of DMABN in MeCN, likewise indicating a similar ICT structure for NTC6 and DMABN. From the decay of the LE absorption and the corresponding growing-in for the ICT state of NTC6, it is concluded that the ICT state originates from the LE precursor and is not formed by direct excitation from S0, nor via an S2/ICT conical intersection. The same conclusion was made from the time-resolved (picosecond) fluorescence spectra, where there is no ICT emission at time zero. The decay of the LE(ESA) band of NTC6 in n-hexane occurs with a shortest time tau2 of 2.2 ps. The ICT reaction is much faster (tau2 = 0.82 ps) in the strongly polar MeCN. The absence of excitation wavelength dependence (290 and 266 nm) for the ESA spectra in MeCN also shows that LE is the ICT precursor. With NIC6 in n-hexane and MeCN, a decay or growing-in of the femtosecond ESA spectra is not observed, in line with the absence of an ICT reaction involving an S2/ICT conical intersection.  相似文献   

17.
Quantum-chemical calculations of the Thioflavin T (ThT) molecule in the ground S0 and first excited singlet S1 states were carried out. It has been established that ThT in the ground state has a noticeable nonplanar conformation: the torsion angle phi between the benzthiazole and the dimethylaminobenzene rings has been found to be approximately 37 degrees. The energy barriers of the intramolecular rotation appearing at phi = 0 and 90 degrees are quite low: semiempirical AM1 and PM3 methods predict values approximately 700 cm-1 and ab initio methods approximately 1000-2000 cm(-1). The INDO/S calculations of vertical transitions to the S1(abs) excited state have revealed that energy ES1(abs) is minimal for the twisted conformation with phi = 90 degrees and that the intramolecular charge-transfer takes place upon the ThT fragments' rotation from phi = 0 to 90 degrees. Ab initio CIS/RHF calculations were performed to find optimal geometries in the excited S1 state for a series of conformers having fixed phi values. The CIS calculations have predicted a minimum of the S1 state energy at phi approximately 21 degrees; however, the energy values are 1.5 times overestimated in comparison to experimental data. Excited state energy dependence on the torsion angle phi, obtained by the INDO/S method, reveals that ES1(fluor) is minimal at phi = approximately 80-100 degrees, and a plateau is clearly observed for torsion angles ranging from 20 to 50 degrees. On the basis of the calculation results, the following scheme of photophysical processes in the excited S1 state of the ThT is suggested. According to the model, a twisted internal charge-transfer (TICT) process takes place for the ThT molecule in the excited singlet state, resulting in a transition from the fluorescent locally excited (LE) state to the nonfluorescent TICT state, accompanied by torsion angle phi growth from 37 to 90 degrees. The TICT process effectively competes with radiative transition from the LE state and is responsible for significant quenching of the ThT fluorescence in low-viscosity solvents. For viscous solvents or when the ThT molecule is located in a rather rigid microenvironment, for example, when it is bound to amyloid fibrils, internal rotation in the dye molecule is blocked due to steric hindrance, which results in suppression of the LE --> TICT quenching process and in a high quantum yield of fluorescence.  相似文献   

18.
The low-frequency (10–450 cm?1) Raman spectra of solid (at 300 K and 130 K) and liquid (at 335 K) 1,4-dimethoxybenzene-d0 and 1,4-dimethoxybenzene-d5 have been measured. The methyl nad methoxyl torsional transitions have been identified and the corresponding torsional barriers calculated. Upon deuleration the methyl torsional barrier is reduced by 450 cm?1, implying a coupling between the methyl torsion and a low-frequency ring mode. As far as the torsions are considered, the internal dynamic situation in 1,4-dimethoxybezene resembles that in amisole. A tentative assignment of the observed lattice bands in given. Certain changes in the spectrum when going from the solid to the melt are attributed to the coexistence of both cis and trans conformers in the liquid state.  相似文献   

19.
Fast and efficient intramolecular charge transfer (ICT) and dual fluorescence is observed with the planarized aminobenzonitrile 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6) in a series of solvents from n-hexane to acetonitrile and methanol. Such a reaction does not take place for the related molecules with 1-isopropyl (NIC6) and 1-methyl (NMC6) groups, nor with the 1-alkyl-5-cyanoindolines with methyl (NMC5), isopropyl (NIC5), or tert-butyl (NTC5) substituents. For these molecules, a single fluorescence band from a locally excited (LE) state is found. The charge transfer reaction of NTC6 is favored by its relatively small energy gap DeltaE(S(1),S(2)), in accordance with the PICT model for ICT in aminobenzonitriles. For the ICT state of NTC6, a dipole moment of around 19 D is obtained from solvatochromic measurements, similar to micro(e)(ICT) = 17 D of 4-(dimethylamino)benzonitrile (DMABN). For NMC5, NIC5, NTC5, NMC6, and NIC6, a dipole moment of around 10 D is determined by solvatochromic analysis, the same as that of the LE state of DMABN. For NTC6 in diethyl ether at -70 degrees C, the forward ICT rate constant (1.3 x 10(11) s(-1)) is much smaller than that of the back reaction (5.9 x 10(9) s(-1)), showing that the equilibrium is on the ICT side. The results presented here make clear that ICT can very well take place with a planarized molecule such as NTC6, when DeltaE(S(1),S(2)) is sufficiently small, indicating that a perpendicular twist of the amino group relative to the rest of the molecule is not necessary for reaching an ICT state with a large dipole moment. The six-membered alicyclic ring in NMC6, for example, prevents ICT by increasing DeltaE(S(1),S(2)) relative to that of DMABN.  相似文献   

20.
Rotationally resolved fluorescence excitation spectroscopy has been used to study the dynamics, electronic distribution, and the relative orientation of the transition moment vector in several vibronic transitions of acenaphthene (ACN) and in its Ar van der Waals (vdW) complex. The 0(0)(0) band of the S(1) ← S(0) transition of ACN exhibits a transition moment orientation parallel to its a-inertial axis. However, some of the vibronic bands exhibit a transition moment orientation parallel to the b-inertial axis, suggesting a Herzberg-Teller coupling with the S(2) state. Additionally, some other vibronic bands exhibit anomalous intensity patterns in several of their rotational transitions. A Fermi resonance involving two near degenerate vibrations has been proposed to explain this behavior. The high-resolution electronic spectrum of the ACN-Ar vdW complex has also been obtained and fully analyzed. The results indicate that the weakly attached argon atom is located on top of the plane of the bare molecule at ~3.48 ? away from its center of mass in the S(0) electronic state.  相似文献   

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