Study of singlet-triplet coupling in glyoxal by level anticrossing spectroscopy. VII. Complete assignment of the 00, 81, 6171 and 41 anticrossing spectra

In paper VI of this series, we have made the statistical analysis of the singlet-triplet coupling matrix elements for ten N_S = 0 singlet vibrational levels of glyoxal, without determining the triplet quantum numbers. In this paper we present the complete assignment (triplet rotational quantum numbers and vibrational symmetry) of each anticrossing observed from four singlet vibrational levels: 0⁰, 8¹, 6¹7¹ and 4¹ (which give respectively 36, 76, 155 and 145 anticrossings by 0 to 7.5 T scans). Therefore we determine the zero-field energy origin of most of the triplet vibrational levels which are located within 7 cm⁻¹ of the four singlet levels studied. Two kinds of selection rules are found: the first stemming from direct vibronic spin-orbit interactions and the second from indirect ones (involving an intermediate triplet state). About half of the anticrossings are due to direct vibronic spin-orbit interactions, the mean value of their matrix elements is more than ten times larger than indirect matrix elements and thus are dominant in ϱ〈V_st〉. In conclusion, we confirm that ISC in glyoxal is governed by direct vibronic spin-orbit interactions.     

Study of singlet-triplet coupling in glyoxal by level anticrossing spectroscopy. VI. Vibrational density and statistics of matrix elements versus energy

By laser excitation of the rotationless level (J = 0) of ten vibrational levels of the S₁ (A_u) state (0⁰, 7², 5¹, 8¹, 6¹7¹, 4¹, 8¹7², 2¹, 8¹4¹ and 2¹7²) of supersonic jet cooled glyoxal, we have obtained S₁-T₁ anticrossing spectra using the homogeneous, high magnetic field (0–8 T) of a Bitter coil. As explained previously, V_st is readily obtained from the width of an anticrossing. As triplet vibrational energy increases from 2776 (0⁰ of S₁) to 4636 cm⁻¹ (2¹7² of S₁), the number of anticrossings increases from 38 (0⁰) to 871 (2¹7²). The anticrossing density is related to the vibrational density of T₁. The V_st histrograms obtained for each vibrational level are very similar: p(V_st) ∝ V^−1−α_st with 0.4 ⩽ α ⩽ 0.7. The more significant and surprising result is that <V_st > is independent of vibrational energy, even though the corresponding vibrational overlaps predicted a decrease in <V_st >, of at least two orders of magnitude between 0⁰ and 2¹7². From V_st statistics we determine ϱ<V_st > and ϱ<V²_st > which are the dominant factors for ISC (intersystem crossing). We predict that strong S-T mixing should occur above 6900 ± 500 cm⁻¹.     

Selected rotational level lifetimes and singlet-triplet coupling in the S1 state of glyoxal

The fluorescence collision-free lifetimes were measured for a few rotational levels of the O° S₁ state of glyoxal using a single-mode Ar⁺ laser. Decays are exponential over 5–6 lifetimes and variation of τ^1.k_o does not exceed 5%. The higher limit of singlet-triplet mixing coefficient β² ? 3 × 10^?2 is deduced from the lifetime measurements. The efficiency of collision induced intersystem crossing and its relation with <β² > value is discussed. ISC is absent in collision-free conditions for deuterated glyoxal as it is known to be for protonated glyoxal.     

Study of the singlet—triplet coupling in glyoxal by level-anticrossing spectroscopy. I. Experimental techniques and results

Level anticrossing and a new optical-radiofrequency double resonance technique were applied to a study of the singlet—triplet interactions for single rotational levels of the vibrationless ¹A_u state of glyoxal. The density and spectral distribution of triplet rotational levels virtually coupled to the (K = 6, J = 13) and (K = 7, J = 35) singlet states were determined. The values of the singlet—triplet coupling constants V_st for some selected level pairs were measured. The assignment to the weak-coupling limit is confirmed.     

Microwave spectroscopic study on the molecular structure and the quadrupole coupling constants of thionyl chloride

Microwave spectra of thionyl chloride, SO³⁵Cl₂ and SO³⁵Cl³⁷Cl, in the frequency range 8–25 GHz have been analyzed. The rotational constants have been obtained from the low J transition frequencies. The r_S coordinates of Cl atoms and the r_o structure have been evaluated with some assumptions: r(S-O) = 1.435 ± 0.011± Å, r(S—Cl) = 2.072 0.005 Å, ∠ OSCl = 108.00 ± 0.06°, ∠ ClSCl = 97.15 ± 0.30°. Nuclear quadrupole coupling constants have been obtained for the SO³⁵Cl₂, species: x_aa = ?25.02 ± 0.04 MHz, x(_bb = ?0.25 ± 0.04 MHz, X_cc = 25.27 ± 0.08 MHz, and X_zz = ?96.75 MHz. The values obtained are compared with those of other workers.     

High resolution probe of spin-orbit coupling and the singlet-triplet gap in chlorocarbene

Among the most important of chemical intermediates are the carbenes, characterized by a divalent carbon that generates low-lying biradical (triplet) and spin-paired (singlet) configurations with unique chemical reactivities. The "holy grail" of carbene chemistry has been determining the singlet-triplet gap and intersystem crossing rates. We report here the first high resolution spectra of singlet-triplet transitions in a prototypical singlet carbene, CHCl, which probe in detail the triplet state structure and spin-orbit coupling with the ground singlet state. Our spectra reveal a pronounced vibrational state dependence of the triplet state spin-spin splitting parameter, which we show is a sensitive probe of spin-orbit coupling with nearby singlet states. The parameters derived from our spectra, including a precise determination of the singlet-triplet energy gap, are in excellent agreement with recent ab initio calculations.     

Nuclear quadrupole coupling constants of thionyl chloride

The nuclear quadrupole structure of some low J transitions with large splittings has been measured for thionyl chloride (SO³⁵Cl₂) and analysed in terms of a first order perturbation. The following nuclear quadrupole coupling constants were obtained: x_aa = ?25.01 ± 0.07 MHz, x_bb = ?0.03 ± 0.45 MHz and x_cc = 25.04 ± 0.45 MHz.     

Microwave spectrum of N2D4, 14N quadrupole coupling constants,and the barrier to inversion of the amino group

The microwave spectrum of N₂D₄ has been observed and analyzed. Based on five low-J rotational transitions the effective rotational constants are: A = 74712.9 ± 1.9 MHz, B = 18500.42 ± 0.46 MHz, and C = 18439.91 ± 0.46 MHz. The quadrupole coupling constants of the ¹⁴N nuclei are X_aa = 4.23 ± 0.04 MHz, X_bb = 1.98 ± 0.05 MHz, and X_cc = ?2.25 ± 0.05 MHz. Using the observed ground state inversion splittings for N₂D₄ and N₂H₄ the barrier to inversion of a single amino group is computed to be 5.00 kcal mol^?1.     

Study of singlet—triplet coupling in glyoxal by level anticrossing spectroscopy. V. Nature of singlet—triplet interaction

We observe in glyoxal cooled in a supersonic free jet the fluorescence of individual rotational levels of the S₁ state excited by a cw laser. We use the technique of singlet—triplet magnetic resonance near an anticrossing to measure matrix elements V₃₁ as a function of rotational quantum numbers N_s, N_t, K_s, K_t. The experimental results are compared with theoretical models of singlet—triplet couplings and we show that the spin-vibronic interaction is the dominant singlet—triplet interaction in glyoxal.     

Microwave spectrum,centrifugal distortion constants,dipole moment and quadrupole coupling constants of pentafluoropyridine

Pentafluoropyridine has been analysed in the frequency range of 8 to 18 GHz at dry ice temperature, using a conventional 100 kHz Stark modulated microwave spectrometer. The rotational constants and centrifugal distortion constants are A = 1481.539 ± 0.003 MHz, B = 1075.348 ± 0.004 MHz and C = 623.101 ± 0.001 MHz; and d_J = ?0.39 ± 0.06 kHz, d_JK = 1.86 ± 0.27 kHz, d_K = 0.70 ± 0.1 kHz, d_EJ = (0.3 ± 0.03) × 10^?6 and d_EK = (?1.5 ± 0.2) × 10^?6. The electric dipole moment has been found to be 0.98 ± 0.08 D and the values of the quadrupole coupling constants are x_aa = 1.94 ± 0.22 MHz, x_bb = ?4.08 ± 0.06 MHz and x_cc = 2.14 ± 0.22 MHz. A simple analysis based on Townes and Dailey theory points to a considerable increase in the π-electron density and excess charge on the nitrogen site.     

Hyperfine interactions in aqueous solution of Cr3+: an ab initio molecular dynamics study

We performed an ab initio molecular dynamics simulation of the paramagnetic transition metal ion Cr³⁺ in aqueous solution. Isotropic hyperfine coupling constants between the electron spin of the chromium ion and nuclear spins of all water molecules have been determined for instantaneous snapshots extracted from the trajectory. The coupling constant of first sphere oxygen, A _iso(¹⁷O_I)=1.9±0.3 MHz, is independent on Cr–O_I distance but increases with the tilt angle for the water molecule approaching 180°. First sphere hydrogen spins have A _iso(¹ H_I)=2.1±0.2 MHz which decreases with increasing tilt angle and shows a Cr–H_I distance dependence. The hyperfine coupling constants for second sphere ¹⁷O is negative and an order of magnitude smaller (−0.20±0.02 MHz) compared to first sphere.     

L-band parallel mode epr. measurement of quadrupole coupling through direct observation of secondary transitions

An L-band (1–2 GHz) EPR spectrometer with static and oscillating magnetic fields parallel is used to obtain quadrupole coupling information through direct measurement of secondary (Δm_s = ±1, Δm₁, = ∓1) transitions. Spectra and interpretations are presented for a test case, ⁶³Cu/Pd(acac)₂ powder, for which QD = 9±1 MHz and QE = 0.6 MHz are obtained.     

Hyperfine structure in the configuration 4f 136s7s of Tm I

Doppler-free saturation absorption spectroscopy was applied on an atomic thulium vapour in a see-through hollow cathode for the determination of precise values for the magnetic dipole hyperfine structure constantsA of 6 levels of the configuration 4f ¹³ 6s7s. A parametric analysis of the hyperfine structure has been performed, using wave-functions from a fine structure calculation, which leads to one-electron hyperfine structure parametersa _4f ⁰¹ =?500(6) MHz,a _6s ¹⁰ =?5058(47) MHz, anda _7s ¹⁰ =?1012 MHz.     

Refinement of the angular dependence of the peptide vicinal NHCαH coupling constant

The refined dependence of the peptide NHCαH vicinal coupling constant on the dihedral angle θ have been derived on the basis of the accumulated experimental data. The mean permissible values (in Hz) are approximated by ³J_NHCH = 9·4 cos² θ - 1·1 cos θ + 0·4 An analogous relationship for the sum of two vicinal NHCαH₂ coupling constants in the glycyl residue have been calculated from the above dependence. Measurements on N-methylacetamide in various solvents and in the presence of an alkali salt showed the vicinal constant NHCH to vary by not more than ± 3%. Some of the other proposed ³J_NHCH(θ) dependencies give too low values for the cis-oriented NH and CαH bonds. This may be due to the fact that in these correlations the data for compounds with cis-amide bonds have been used for 0° ? θ ? 90° region of the dependence.     

The rotational spectrum,nuclear spin—spin coupling,nuclear quadrupole coupling,and molecular structure of KrHF

Rotational spectra have been assigned for the ⁸²Kr, ⁸³Kr, ⁸⁴Kr, and ⁸⁶Kr isotopic species of the KrHF and KrDF van der Waals molecules by using pulsed microwave Fourier transform spectroscopy in a Fabry—Perot cavity with a pulsed supersonic nozzle molecular source. The rotational, centrifugal distortion, nuclear spin—spin, and nuclear quadrupole coupling constants are used to determine the structure and obtain intramolecular potential binding information. The ⁸³Kr nuclear quadrupole coupling constants are 10.28 ± 0.08 MHz and 13.83 ± 0.13 MHz for KrHF and KrDF respectively. The electric field gradient at the krypton nucleus is calculated from the coupling constant and the known nuclear quadrupole moment and explained by Sternheimer shielding and formation of the van der Waals bond. There is a negligible charge transfer in the KrHF bond.     

A test of the accuracy of atomic-beam laser spectroscopy

To determine the accuracy to which hyperfine splittings can be measured using a cw dye laser with rf sideband tuning, a series of atomic beam experiments with⁵⁹Co was performed. One hyperfine splitting of the first excited metastable atomic state was measured and compared with the results for the same splitting from magnetic rf resonance experiments. The uncertainty with the methods applied was found to be about 0.05 to 1% of the experimental linewidth in general; it is ±20 kHz or ±0.05% of the linewidth in the present Co experiment. The hyperfine splitting constants of the 3d ⁸ 4p ² F _7/2 state were found to beA=419.3(9) MHz,B=?77(17) MHz.     

Study of singlet-triplet transitions in the ozone molecule using the multiconfigurational self-consistent field theory

The intensities and dipole moments of the lower singlet-triplet transitions ³ A ₂ ← X ¹ A ₁ and ³ B ₁ ← X ¹ A ₁ in the ozone molecule were calculated by the multiconfiguration self-consistent field theory with the quadratic response function. The results of calculations of the intensities of singlet-triplet transitions using different basis sets and complete active spaces were compared. The assignment of the ³ A ₂ ← X ¹ A ₁ transition in the ozone spectrum to the Wulf band is discussed.     

Test of advanced hyperfine structure theory by precision radio-frequency and laser spectroscopy in molybdenum

The hyperfine structure splittings of 32 even parity states and of 26 odd partity states of molybdenum have been measured by atomic beam magnetic resonance and by laser induced fluorescence. The analysis of the hyperfine structure data of the even parity configurations (4d+5s)⁶ yields experimental evidence for second order hyperfine interactions. In addition, theg _J factors of 19 fine structure levels have been determined in order to test the quality of intermediate coupling wave functions for the (4d+5s)⁶ configurations.     

Nuclear spin-spin coupling in the spectrum of I2 at 6328 Å

The effects of nuclear spin-spin coupling are included in the analysis of the nuclear hyperfine structure of the R(127) line of the 11-5 band in the B-X electronic band system of I₂. The fit to the experimental data is improved over earlier fits in which only the effects of nuclear spin-rotation interaction and nuclear electric quadrupole coupling were considered. The electron-coupled contribution to the spin-spin constant of the upper state is determined to be d_E = ?36.3 ± 8.5 kHz. However, the fit (standard deviation = 59.8 kHz) is still not at the level of the experimental precision (40 kHz) and further measurements are in progress to test the model used for the hfs hamiltonian.     

Spectroscopic properties of the Ar 2 * (5p) excimer states

The transitions between Ar ₂ ^* (5p) and Ar ₂ ^* (4sΣ _u) have been investigated by absorption spectrometry. The fine structure of the Ar ₂ ^* (5p ³ Π _g) was attributed to a predominantly Hund’s case a coupling. A spin orbit coupling constant of A = (9.8±0.3) cm^-1 results. Absorption by the singlet system allows one to determine the triplet/singlet splitting between the Ar ₂ ^* (4s Σ _u) states to be (540 ± 100) cm^-1. The transition probabilities of the Ar ₂ ^* (5p) and Ar ₂ ^* (6p) levels were determined by saturation spectrometry yielding values between (0.2–2.5) · 10⁶ s^-1.