Temperature effects on the phosphorescence spectra and lifetimes of 2,4-, 2,5-, and 3,4-dimethylbenzaldehydes dispersed in durene single crystals

The phosphorescence spectra and lifetimes of 2,4-, 2,5-, and 3,4-dimethylbenzaldehydes dispersed in durene single crystals have been measured as a function of temperature between 10 and 200 K. For all the guests involved, the vibrational structures of the spectra are found to be temperature dependent. This is interpreted in terms of two emissions that proceed from a triplet state having predominantly a ππ* character at low temperatures and from a thermally populated triplet state having essentially a nπ* character at higher temperatures. The energy gaps ΔE_T between ³ππ* and ³nπ* states evaluated spectroscopically are found to be 100, 70, and 340 cm^?1, respectively for 2,4-, 2,5- and 3,4-dimethylbenzaldehydes.Activation energies ΔE* determined from the Arrhenius plots of the phosphorescence decay rate constants are in good agreement with the ΔE_T for the first two guests. In contrast, the ΔE* are higher than the ΔE_T for 3,4-dimethylbenzaldehydes as well as for 2,4,5-trimethylbenzaldehyde (where ΔE_T ≈ 400 cm^?1) because of the rapid increase of radiationless transitions in the temperature range where thermal population of the upper ³nπ* state is efficient. In the low and high temperature ranges, the phosphorescence decays for all these guests are exponential. In the intermediate range, these decays are non-exponential. The origin of these non-exponential decays is discussed.     

ESR study of the photoexcited triplet state of substituted 2-acetonaphthones

Electron spin resonance of phosphorescent triplet states of a number of 6-substituted-2-acetonaphthones is studied at 77 K in toluene glass. The life-times of the triplet states and zero-field parameter D* have been measured from Δm_s = ± 2 resonance. The life-times and the zero-field splitting parameters indicate that the lowest triplet states have mainly π, π* character.     

ELECTRON TRANSFER FROM PHOTOEXCITED SINGLET AND TRIPLET BACTERIOPHEOPHYTIN—II. THEORETICAL

Abstract— A previous paper showed that collision of the first excited singlet state of bacteriopheophytin (Bph*) and p-benzoquinone (Q) returns Bph* to the ground state; however, excited triplet (Bph⁺) and quinone on collision produce the radical ions, (Bph⁺) and (Q^?). This paer rationalizes these findings by first estimating the half cell potentials Bph⁺/Bph* and Bph⁺/Bph^T, the energy for the various collision complexes, and the energy of the charge separated ions Bph⁺+ Q? and then estimating the rates for conversion among these various states. Thus it is estimated that the complexes [Bph*Q] or [Bph^TQ], live ?5 ps before dissociating. This is long enough for electron transfer to occur, producing the singlet and triplet charge transfer complexes, [Bph⁺Q?]^S or [Bph⁺Q?]^T, either of which could separate to Bph⁺+ Q? in ?230ps. In the singlet case, quenching by reverse charge transfer [Bph⁺Q?]^S→[Bph Q] occurs more rapidly than ion separation; however, the analogous triplet process, [Bph⁺Q?]^T→ [Bph Q], is spin forbidden, so that ion separation competes successfully with quenching. Spin scrambling, [Bph⁺Q?]^S? [Bph⁺Q?]^T, is estimated to be slow, as this explanation requires. In the bacterial photosynthetic reaction center, the initial electron transfer from an excited singlet state of the bacteriochlorophyll dimer complex (BB)* to bacteriopheophytin, giving [(BB⁺)(Bph?)]^S, successfully leads to ion separated species (i) because reverse charge transfer [(BB⁺)(Bph?)]^S→ [(BB)(Bph)] is slowed by a fairly large Franck-Condon energy, ΔE? lev, which is difficult to convert from electronic to vibrational degrees of freedom and (ii) because of the rapid subsequent electron transfer from (Bph⁺) to another acceptor X.     

Excess properties and spectroscopic studies of binary system 1,4-butanediol + water at T = (293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K

Density and dynamic viscosity data were measured over the whole concentration range for the binary system 1,4-butanediol (1) + water (2) at T = (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K as a function of composition under atmospheric pressure. Based on density and dynamic viscosity data, excess molar density (ρ^E), dynamic viscosity deviation (Δν) and excess molar volume (V_m^E) were calculated. From the dynamic viscosity data, excess Gibbs energies (ΔG*^E), Gibbs free energy of activation of viscous flow (ΔG*), enthalpy of activation for viscous flow (ΔH*) and entropy of activation for viscous flow (ΔS*) were also calculated. The ρ^E, V_m^E, Δν and ΔG*^E values were correlated by a Redlich?Kister-type function to obtain the coefficients and to estimate the standard deviations between the experimental and calculated quantities. Based on FTIR and UV spectral results, the intermolecular interaction of 1,4-butanediol with H₂O was discussed.     

EPR spectroscopy of multicomponent,multispin molecular system obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon

Complex multicomponent, multispin molecular system, consisting of a septet trinitrene, two quintet dinitrenes, and three triplet mononitrenes, was obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon. To identify these paramagnetic products, electron paramagnetic resonance spectroscopy in combination with line-shape spectral simulations and density functional theory calculations was used. The products of the photolysis was found to be triplet 2,4-diazido-3-cyano-5-fluoropyridyl-6-nitrene (D_T = 1.000 cm⁻¹, E_T = 0), triplet 2,4-diazido-3-cyano-5-fluoropyridyl-2-nitrene (D_T = 1.043 cm⁻¹, E_T = 0), triplet 2,6-diazido-3-cyano-5-fluoropyridyl-4-nitrene (D_T = 1.128 cm⁻¹, E_T = 0 cm⁻¹), quintet 4-azido-3-cyano-5-fluoropyridyl-2,6-dinitrene (D_Q = 0.211 cm⁻¹, E_Q = 0.0532 cm⁻¹), quintet 2-azido-3-cyano-5-fluoropyridyl-4,6-dinitrene (D_Q = 0.208 cm⁻¹, E_Q = 0.0386 cm⁻¹), and septet 3-cyano-5-fluoropyridyl-2,4,6-trinitrene (D_S = −0.1017 cm⁻¹, E_S = −0.0042 cm⁻¹) in a 38:4:7:22:14:4 ratio, respectively.     

Direct Observation of an Imidoylnitrene: Photochemical Formation of PhC(=NMe)−N and Me−N from 1‐Methyl‐5‐phenyltetrazole

The imidoylnitrene 8 , N‐methyl‐C‐phenylimidoylnitrene, has been generated by laser photolysis of 1‐methyl‐5‐phenyltetrazole 6 at 5 K and characterized by its ESR spectrum (|D/hc|=0.9602, |E/hc|=0.0144 cm^?1). In addition, the triplet excited states of 6 and of 2‐methyl‐5‐phenyltetrazole 11 were also observed by ESR spectroscopy in the 5 K matrices ( 6 : |D/hc|=0.123 cm^?1, E/hc=0.0065 cm^?1, 11 : |D/hc|=0.126 cm^?1, |E/hc|=0.0056 cm^?1). The imidoylnitrene 8 is unstable both thermally (disappearing at 80 K) and photochemically (disappearing on continued irradiation at 266 nm). Methyl(phenyl)carbodiimide is the end product of photolysis.     

STEREOELECTRONIC PROPERTIES OF PHOTOSYNTHETIC AND RELATED SYSTEMS—VII. AB INITIO QUANTUM MECHANICAL CHARACTERIZATION OF THE ELECTRONIC STRUCTURE AND SPECTRA OF CHLOROPHYLLIDE a AND BACTERIOCHLOROPHYLLIDE a CATION RADICALS

Abstract— Ab initio configuration interaction wavefunctions and energies are reported for 29 doublet states and three quartet states of the cation radicals of ethyl chlorophyllide a (Et-Chl a⁺) and ethyl bacteriochlorophyllide a (Et-BChl a⁺). In Et-Chl a.⁺ I the lowest excited doublet state D₁ is estimated to lie 5220 cm^-1 above the ground state D₀, with a negligibly small D₁← D₀ transition probability. The lowest quartet state, Q₁, is estimated to lie 7980 cm^-1 above D₁. The absorption spectrum up to 20,000cm^-1 is shown to consist primarily of numerous low-intensity ‘background’ transitions, with transitions to D₅ and D₁₁ accounting for the observed peaks at 12,200cm^-1 and 17,500cm^-1, respectively. The large intense band at 25,000cm^-1 is due primarily to transitions to D₂₂ and D₂₃, with numerous lower-intensity transitions to neighboring states. In Et-BChl a.⁺ D₁ is estimated to lie 7112 cm-¹ above D₀, and Q, is approximately 5725 cm^-1 above D. A pair of states, D₃ and D₅, account for the absorption at 11,000 cm^-1, while another pair of states, D₁₃ and D₁₄, are associated with the broad, weak absorption near 20,000 cm^-1. The two prominent intense peaks at 23,700 cm^-1 and 27,700 cm^-1 are assigned to D₂₃ and D₂₈, respectively, while the shoulder located at 25,500cm^-1 is attributed to transitions to D₂₄ and D₂₆. As in Et-Chl at, numerous background transitions are found throughout the spectrum. The π spin density distribution in D₀ of both molecules is similar, with spin density found predominantly on the α-carbon atoms. In both systems, approximately 65% of the π spin density in D₁ is found on the methine carbon atoms, with the remainder found largely on the nitrogen atoms.     

A CAS study on S‐loss and O‐loss dissociation mechanisms of the SO2+ ion in the C,D, and E states

In the present work, we mainly study dissociation of the C ²B₁, D²A₁, and E²B₂ states of the SO₂⁺ ion using the complete active‐space self‐consistent field (CASSCF) and multiconfiguration second‐order perturbation theory (CASPT2) methods. We first performed CASPT2 potential energy curve (PEC) calculations for S‐ and O‐loss dissociation from the X, A, B, C, D, and E primarily ionization states and many quartet states. For studying S‐loss predissociation of the C, D, and E states by the quartet states to the first, second, and third S‐loss dissociation limits, the CASSCF minimum energy crossing point (MECP) calculations for the doublet/quartet state pairs were performed, and then the CASPT2 energies and CASSCF spin‐orbit couplings were calculated at the MECPs. Our calculations predict eight S‐loss predissociation processes (via MECPs and transition states) for the C, D, and E states and the energetics for these processes are reported. This study indicates that the C and D states can adiabatically dissociate to the first O‐loss dissociation limit. Our calculations (PEC and MECP) predict a predissociation process for the E state to the first O‐loss limit. Our calculations also predict that the E²B₂ state could dissociate to the first S‐ and O‐loss limits via the A²B₂ ← E²B₂ transition. On the basis of the 13 predicted processes, we discussed the S‐ and O‐loss dissociation mechanisms of the C, D, and E states proposed in the previous experimental studies. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

High-resolution photofragment translational spectroscopy for the UV photodissociation of C<Subscript>2</Subscript>H<Subscript>5</Subscript>I

The photodissociation of ethyl iodide at 279.71, 281.73, 304.02 and 304.67 nm has been studied on our new mini-photofragment translational spectrometer with a total flight path of only 5 cm. Some vibrational peaks are firstly resolved in the TOF spectra of I*(2P1/2) and I(2P3/2) channels. These vibrational peaks are assigned to the excitation states (v2 = 0, 1, 2,…) of the umbrella mode (v2, 540 cm-1) of the photofragment C2H5, and the distribution of the vibrational states is obtained. The dissociation energy has been determined to be D0(C-I)=2.314 ±0.03 eV. The energy partitioning of the available energy (Eavl=ET Eint=ET EV,R) calculated from our experimental data (-E)int/Eavl= 22.1% at 281.73 nm, 22.4% at 304.02 nm for the I* channel, and (-E)int/Eavl = 25.2% at 279.71 nm, 25.9% at 304.67 nm for the I channel, seem to be more reliable.     

Evidence for long-lived excited states of [CnH2]2+ carbodications

The energetics, structures, stabilities and reactivities of[C_nH₂]²⁺ ions have been investigated using computational methods and experimental mass spectrometric techniques. Spontaneous decompositions of [C_nH₂]²⁺ into [C_nH]⁺ + H⁺ products, observed for ions with odd-n values, have been explained by invoking the formation of excited triplet states. Even-n [C_nH]⁺ ions possess triplet ground states with low-lying excited states, whereas odd-n ions have triplet states with energies several eV above ground singlet states. Radiationless transitions of vibrationally excited long-lived triplet state ions into singlet state continua are suggested as possible mechanisms for spontaneous deprotonation processes of odd-n [C_nH₂]²⁺ ions. Evidence for these long-lived excited states has been obtained in bimolecular single electron transfer reactions.     

Molecular constants for the ã 3A2 state of formaldehyde

The 0⁺–0 and 1⁺–0 bands of the ā ³A₂X? ¹A₁ transition of formaldehyde have been reinvestigated using higher resolving power than was available in the earlier work of Raynes. The rotational analyses have been considerably extended, and improved molecular constants for the ā ³A₂ state have been obtained with the aid of a new triplet—singlet computer programme.^sSR branches of the K′ = 7K″ = 5 and K′ = 5K″ = 3 subbands have been observed in the 0⁺–0 band using 7m atm of absorbing gas. These results provide the first example of the observation of ΔK = ±2 transitions in triplet—singlet bands of a polyatomic molecule. The “perpendicular” transition moment is found to be about 10% of the “parallel” transition moment.     

Untersuchung reversibler Photoprozesse durch Blitzlichtphotolyse IV. Triplettzustände des 1, 3, 6′, 8′- tetramethyl-dehydrodianthrons

By means of the flash photolysis technique, transient absorption spectra attributed to tetramethyl-dehydrodianthrone (TMD) in both the photochromic and triplet states have been investigated in polymethylmethacrylate matrices and in the solvent triacetin. In polymethylmethacrylate matrices and in rigid glasses of triacetin the triplet state of TMD is heavily populated. Triplet-triplet absorption and phosphorescence measurements show that below 180°K the triplet decay follows first order kinetics with the decay constant k=11,3 ± 0,1 s^?1. In incompletely solidified triacetin glass it is possible to monitor the transient absorption of the photochromic and the triplet state simultaneously. It is shown that the photochromic state ¹A₁* is not generated via the triplet state. Therefore the authors suggest a kinetic scheme characterised by a direct singlet state - photochromic state transition.     

NMR of Terminal Oxygen. Part 13. 17O-NMR spectra of C-nitroso compounds,thionitrites and NO+ Ion: Resonance effects in ON—X compounds and correlation with CD spectra

The ¹⁷O-NMR signals of four true C-nitroso compounds 1–4 appear at particularly low field (1550–1265 ppm), whereas the dimers (azodioxy type) resonate at ca. 400 ppm and the ‘isonitroso compounds’ ( ? quinone-oximes; 5 and 6 ) at ca. 250 ppm. S-Nitroso compounds ( ? thionitrites; 8 and 9 ) show shift values of ca. 1300 ppm, not far from C—NO; the NO⁺ ion is much stronger shielded (474 ppm). The results, together with those for higher-shielded nitroso compounds X—NO (X ? RO, R₂N, Cl, O^?) are discussed in terms of (a) resonance stabilization through n-donation from X(π-bond order, approximated by the known barriers of rotation around the X—N bond) and of (b) electronic excitation energies ΔE. The latter are approximated by long-wave (symmetry-forbidden) UV/VIS absorptions and confirmed, where available, by the maxima of the curves of circular dichroism (CD); the CD curve of thionitrite 9 has been measured. It is found that the δ(¹⁷O) values of X—NO depend both on bond order and on ΔE, which could not be separated. The higher shielding of NO⁺ compared with X—N?O is explained on the basis of anisotropy effects, which differ between sp and sp² systems.     

Polarographic study of the effect of solvents on the reaction of Na amalgam with some vinyl monomers

Acrylonitrile, methacrylonitrile, ethyl acrylate, anthracene, and Na⁺ were studied polarographically in four solvent media: diglyme, DMSO, 25% H₂O in diglyme, and liquid NH₃. Cathodic shifts were observed for Na⁺ and anodic shifts for the vinyl monomers in DMSO, H₂O and NH₃. The values of ΔE = (E_{1/2, monomer} — E_{1/2, Na}⁺) were used in interpretation of the solvent effects observed previously for the reaction of these monomers with Na amalgam. In diglyme ΔE is very large (0.49 V for MeAN and 0.37 V) for AN, and therefore very slow reaction takes place. In DMSO, MeAN still reacts very slowly (ΔE = 0.23 V), while AN (ΔE = 0.09 V) reacts considerably faster than in diglyme and 100 times faster than MeAN in DMSO. Liquid ammonia brings both MeAN and AN to very low ΔE (0.08 V and ?0.05 V, respectively), and both reactions are very fast and yield only the hydrodimers. Water, on the other hand, has a large accelerating effect on the rate, but as it is a proton donor it yields only the reduced products.     

The relative signs of the zero-field parameters from phosphorescence-microwave double resonance (PMDR) spectroscopy: 1, 2, 4, 5 tetrachlorobenzene

It is shown that the relative signs of D and E as well as the assignment of the symmetry of the electronic spatial wavefunction of the lowest emitting triplet state can be made at very low temperatures by determining the polarized amplitude modulated phosphorescence-microwave double resonance (AM-PMDR) spectrum, the lifetimes of the individual zero-field (zf) levels, and the polarization of the crucial magnetic zf transition. The technique is applied to 1, 2, 4, 5 tetrachlorobenzene. D and E are found to be of the same sign, and the lowest triplet state is found to be of ³B_1u symmetry. In going from benzene to its tetrachloro-derivative, the absolute value of D decreases by only a few percent, while that for E increases by ≈400%.     

Correlation of activation energies of radical–molecule metathesis reactions with enthalpic,polar, and steric parameters

It is shown that the activation energies E oF chlorine atom abstraction by cyclohexyl radicals and hydrogen atom abstraction by Cl atoms from polychloroalkanes can be correlated with the bond dissociation energies D and the Taft polar and steric substituent constants σ* and E_s by the expression: where ΔE and ΔD represent the differences between the E and D values of a given substrate and those of a reference compound (CH₃ substituted substrate) and α, ρ, and δ are the corresponding correlation coefficients. The use of this expression allows quantitative evaluation of the relative contribution of the various factors affecting the activation energies of these reactions and estimation of related thermochemical data.     

Identification of Δn≠0 quintet transitions in four-electronF 5+

Two Δn≠0 quintet transitions, 1s 2s 2p ^{2 5} P—1s 2s 2p 3d ⁵ P ⁰,⁵ D ⁰, have been identified in the beam-foil spectra of fluorine. The wavelengths are compared to theoretical predictions and to those of singly-excited five-electron ions.     

The first experimental observation of electronic transitions in C2+ and C2D+

High-resolution translational energy spectroscopy (up to 0.1 eV) has been carried out on 8 kV of C₂⁺ and C₂D⁺. The spetra obtained with C₂⁺ formed by different methods show considerable differences which are attributed to the formation of different spin states of the ion. Tentative assignments for the observed transitions have been made including one corresponding to excitation of the ⁴∑_g^? —X ⁴∑_g^? system, which may be useful as a probe of interstellar C₂⁺. Two broad transitions have been seen in the translational energy spectrum of C₂D⁺ which are in reasonable agreement with existing theoretical calculations. Tentative assignments are proposed for these transitions.     

Ab initio study of reactions of hydroxyl radicals with chloro‐ and fluoro‐substituted methanes

Ab initio calculations at the unrestricted Hartree–Fock (UHF) level have been performed to investigate the hydrogen abstraction reactions of ^? OH radicals with methane and nine halogen‐substituted methanes (F, Cl). Geometry optimization and vibrational frequency calculations have been performed on all reactants, adducts, products, and transition states at the UHF/6‐31G* level. Single‐point energy calculations at the MP2/6‐31++G* level using the UHF/6‐31G* optimized geometries have also been carried out on all species. Pre‐ and postreaction adducts have been detected on the UHF/6‐31G* potential energy surfaces of the studied reactions. Energy barriers, ΔE^?, reaction energies, ΔE_r, reaction enthalpies, ΔH_r, and activation energies, E_a, have been determined for all reactions and corrected for zero‐point energy effects. Both E_a and ΔH_r come into reasonable agreement with the experiment when correlation energy is taken into account and when more polarized and diffuse basis sets are used. The E_a values, estimated at the PMP2/6‐31++G* level, are found to be in good agreement with the experimental ones and correctly reproduce the experimentally observed trends in fluorine and chlorine substitution effects. A linear correlation between E_a and ΔH_r is obtained, suggesting the presence of an Evans–Polanyi type of relationship. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 426–440, 2001     

Ab initio study on the reaction of Sc+ + CH4 → Sc+(SINGLE BOND)CH2 + H2

An ab initio study on the reaction of the ground state (³D) and the excited state (¹D) of Sc⁺ with methane was performed. Reaction channels on the singlet and triplet potential surface (PES) and the reaction mechanism are examined and discussed. Three regions of the potential surface was studied: the molecular complex, the C(SINGLE BOND)H insertion products, and the transition states for the reaction. Comparisons between singlet and triplet PESs show that the excited state (¹D) of Sc⁺ has more reactivity with methane than does the ground state (³D) due to the spin quantum number conservation with the more stable insertion intermediate. © 1997 John Wiley & Sons, Inc.