Electronic states of neutral and cationic bis(benzene) titanium and vanadium sandwich complexes studied by pulsed field ionization electron spectroscopy

Bradford R. Sohnlein; Yuxiu Lei; Dong Sheng Yang

doi:10.1063/1.2771158

Electronic states of neutral and cationic bis(benzene) titanium and vanadium sandwich complexes studied by pulsed field ionization electron spectroscopy

Bradford R. Sohnlein, Yuxiu Lei, Dong Sheng Yang

Chemistry

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

Abstract

Ti- and V- bz2 (bz= C6 H6) sandwich complexes have been prepared in a laser-ablation cluster beam source and studied by pulsed field ionization-zero electron kinetic energy photoelectron spectroscopy and theoretical calculations. The ground electronic states of the neutral Ti- and V- bz2 complexes are determined to be A 1g 1 and A 1g 2, and their ionization energies are measured to be 5.732±0.001 and 5.784±0.002 eV, respectively. These neutral complexes have 6 binding and are in an eclipsed D6h configuration with flat benzene rings. Ionization of the A 1g 1 and A 1g 2 neutral states of Ti- and V- bz2 yields the B 1g 2 and B 1g 3 ion states, respectively, in a D2h point group with slightly puckered benzene rings. In addition, the binding and structures of these two complexes are compared with other first-row transition metal bis(benzene) sandwiches.

Original language	English
Article number	114302
Journal	Journal of Chemical Physics
Volume	127
Issue number	11
DOIs	https://doi.org/10.1063/1.2771158
State	Published - 2007

Bibliographical note

Funding Information:
We gratefully acknowledge financial support from the Experimental Physical Chemistry Program of the National Science Foundation. We also acknowledge additional funding from the Petroleum Research Fund of the American Chemical Society and Kentucky Science and Engineering Foundation. Table I. Electronic states, point groups (PGs), bond lengths ( R , Å), dihedral angle (∠, degrees), symmetric metal-benzene stretches ( ν s + ∕ ν s , cm − 1 ), and relative electronic energies ( E ele , cm − 1 ) of eclipsed Ti– and V – bz 2 sandwich complexes from B 3 LYP ∕ 6 - 311 + G ( d , p ) calculations. The predicted free benzene structure is also given at this level of theory. Electronic energies in parentheses are from CCSD(T) single-point energy calculations. State a PG R M – C R C – C ∠ C – C – C – C ν s + ∕ ν s E ele Ti – bz 2 A 1 g 1 D 6 h 2.27 1.42 0 245 0 B 1 g 3 D 2 h 2.36, 2.31 1.40, 1.43 6 214 2193 (4682) A u 5 D 2 h 2.44, 2.41 1.43, 1.39 3 190 12 744 Ti + – bz 2 228 b A 1 g 4 D 6 h 2.43 1.41 0 183 42 323 (43 704) B 1 g 2 D 2 h 2.35, 2.29 1.40, 1.42 6 223 43 807 (44 204) V – bz 2 A 1 g 2 D 6 h 2.22 1.42 0 250 0 A 4 C 1 2.31, 2.22,2.32, 2.82,2.34, 2.26 1.39, 1.44,1.43, 1.40,1.37, 1.45 11, 1,10, 23 228 12 532 A 6 c C 1 2.31, 3.00,3.56, 2.38,2.41, 2.46 1.43, 1.42,1.39, 1.41 1 219 17 843 V + – bz 2 231 b B 1 g 3 D 2 h 2.25, 2.31 1.40, 1.42 6 219 43 675 A 1 g 1 D 6 h 2.21 1.42 0 253 50 851 bz A 1 g 1 D 6 h 1.39 0 a Electronic symmetry species of all states are labeled with the same Cartesian coordinate system used in D 6 h point group. In DFT calculations with GAUSSIAN software the B 1 g symmetry species was incorrectly labeled as B 3 g . b From ZEKE spectra. c Slipped sandwich structure. Table II. Peak positions and assignments for the ZEKE spectra of Ti– and V – bz 2 complexes. s stands for the symmetric metal-benzene stretching mode, t stands for the benzene torsion mode, and b stands for the C–H out-of-plane bending mode. Ti – bz 2 V – bz 2 B 1 g 2 ← A 1 g 1 B 1 g 3 ← A 1 g 2 Position a Assignment Position a Assignment 46 228 Origin 46 655 Origin 46 240 t 0 2 46 885 s 0 1 46 456 s 0 1 47 115 s 0 2 46 470 s 0 1 t 0 2 47 347 s 0 3 46 684 s 0 2 47 576 s 0 4 46 697 s 0 2 t 0 2 46 910 s 0 3 46 921 s 0 3 t 0 2 46 971 b 0 1 47 137 s 0 4 47 149 s 0 4 t 0 2 47 197 b 0 1 s 0 1 47 363 s 0 5 47 377 s 0 5 t 0 2 47 421 b 0 1 s 0 2 47 590 s 0 6 47 601 s 0 6 t 0 2 a The uncertainties in peak positions are ∼ 8 cm − 1 for the Ti – bz 2 B 1 g 2 ← A 1 g 1 transition and ∼ 15 cm − 1 for the V – bz 2 B 1 g 3 ← A 1 g 2 transition. Table III. Electronic transition energies ( T 00 , eV) and vibrational frequencies ( cm − 1 ) of the Ti– and V – bz 2 sandwich complexes from ZEKE spectra and B 3 LYP ∕ 6 - 311 + G ( d , p ) calculations. Ionization energies from previous measurements are listed for the purpose of comparison. ZEKE B3LYP PES PIE Rydberg Ti – bz 2 T 00 B 1 g 2 ← A 1 g 1 5.732(1) 5.48 a 5.5–6.0 b 5.71(2)/5.68(4) c ν s + C 6 H 6 – Ti + – C 6 H 6 stretch 228 223 ν b + C–H out-of-plane bend 741 766 V – bz 2 T 00 B 1 g 3 ← A 1 g 2 5.784(2) 5.46 a 5.95 d 5.75(3) e 6.16(2) f ν s + C 6 H 6 – V + – C 6 H 6 stretch 230 219 a With zero-point vibrational energy corrections. b Reference 6 . c References 4 and 5 . d References 6 and 8 . e References 5 and 7 . f Reference 9 . Table IV. Electronic transitions ( T 00 ) and point groups, ionization energies (IE, eV), M + ∕ M – C distances (Å), symmetric M + – bz 2 stretch frequencies ( ν s + , cm − 1 ), and dissociation energies ( D o and D o + , eV) for M + ∕ M – bz 2 ( M = Sc – Cr ) complexes. IEs and ν s + are from ZEKE spectra, M + ∕ M – C distances from B3LYP calculations, D 0 + from mass spectrometry-based measurements, and D 0 from thermochemical cycles. Sc – bz 2 a Ti – bz 2 V – bz 2 Cr – bz 2 b Transition c A g 1 ← B 1 g 2 A 1 g 3 ← B 1 g 2 B 1 g 2 ← A 1 g 1 B 1 g 3 ← A 1 g 2 A 1 g 2 ← A 1 g 1 Point group D 2 h ← D 2 h D 6 h ← D 2 h D 2 h ← D 6 h D 2 h ← D 6 h D 6 h ← D 6 h IE 5.069 (3) 5.221 (1) 5.732 (1) 5.784 (2) 5.465 (1) M–C 2.44, 2.39 2.44, 2.39 2.27 2.22 2.18 M + – C 2.50, 2.40 2.49 2.35, 2.29 2.25, 2.31 2.19 ν s + 206 201 228 230 264 D o + d 4.2 (2) 5.3 (2) 5.0 (2) 4.2 (2) D o e 2.7 (2) 4.2 (2) 4.0 (2) 2.9 (2)2.8 (2) f a Reference 16 . b Reference 13 . c Electronic symmetry species of all states are labeled with the same Cartesian coordinate system used in D 6 h point group. In DFT calculations with GAUSSIAN software the B 1 g symmetry species was incorrectly labeled as B 3 g . d D o + for M + – bz 2 → M + + 2 bz . D 0 + ( Sc + – bz 2 ) is from Ref. 40 by assuming that the dissociation energy of Sc – bz 2 is twice as that of Sc–bz. D 0 + of the other complexes are from Ref. 39 . e D o = D o + − IE ( M – bz 2 ) − IE ( M ) for M – bz 2 → M + 2 bz . f From threshold photoelectron-photoion coincidence spectroscopy (Ref. 42 ). FIG. 1. PIE spectra of Ti – bz 2 (a) and V – bz 2 (b) complexes seeded in helium carrier. The ionization thresholds are indicated by the vertical arrows. FIG. 2. Experimental ZEKE spectrum in helium carrier (a) and B3LYP simulations ( 150 K ) of spin-allowed transitions of eclipsed Ti – bz 2 [(b)–(d)]. FIG. 3. Relative energies of the electronic states of Ti + ∕ Ti – bz 2 predicted at the B 3 LYP ∕ 6 - 311 + G ( d , p ) level of theory. The spin-allowed transitions [ Δ ( 2 S + 1 ) = ± 1 ] are indicated by the vertical arrows. FIG. 4. Experimental ZEKE spectrum in helium carrier (a) and B3LYP simulations ( 150 K ) of spin-allowed transitions of eclipsed V – bz 2 [(b)–(c)].

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Physical and Theoretical Chemistry

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10.1063/1.2771158

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@article{5a241efbc73c4120bd8b7e7468d854bc,

title = "Electronic states of neutral and cationic bis(benzene) titanium and vanadium sandwich complexes studied by pulsed field ionization electron spectroscopy",

abstract = "Ti- and V- bz2 (bz= C6 H6) sandwich complexes have been prepared in a laser-ablation cluster beam source and studied by pulsed field ionization-zero electron kinetic energy photoelectron spectroscopy and theoretical calculations. The ground electronic states of the neutral Ti- and V- bz2 complexes are determined to be A 1g 1 and A 1g 2, and their ionization energies are measured to be 5.732±0.001 and 5.784±0.002 eV, respectively. These neutral complexes have 6 binding and are in an eclipsed D6h configuration with flat benzene rings. Ionization of the A 1g 1 and A 1g 2 neutral states of Ti- and V- bz2 yields the B 1g 2 and B 1g 3 ion states, respectively, in a D2h point group with slightly puckered benzene rings. In addition, the binding and structures of these two complexes are compared with other first-row transition metal bis(benzene) sandwiches.",

author = "Sohnlein, {Bradford R.} and Yuxiu Lei and Yang, {Dong Sheng}",

note = "Funding Information: We gratefully acknowledge financial support from the Experimental Physical Chemistry Program of the National Science Foundation. We also acknowledge additional funding from the Petroleum Research Fund of the American Chemical Society and Kentucky Science and Engineering Foundation. Table I. Electronic states, point groups (PGs), bond lengths ( R , {\AA}), dihedral angle (∠, degrees), symmetric metal-benzene stretches ( ν s + ∕ ν s , cm − 1 ), and relative electronic energies ( E ele , cm − 1 ) of eclipsed Ti– and V – bz 2 sandwich complexes from B 3 LYP ∕ 6 - 311 + G ( d , p ) calculations. The predicted free benzene structure is also given at this level of theory. Electronic energies in parentheses are from CCSD(T) single-point energy calculations. State a PG R M – C R C – C ∠ C – C – C – C ν s + ∕ ν s E ele Ti – bz 2 A 1 g 1 D 6 h 2.27 1.42 0 245 0 B 1 g 3 D 2 h 2.36, 2.31 1.40, 1.43 6 214 2193 (4682) A u 5 D 2 h 2.44, 2.41 1.43, 1.39 3 190 12 744 Ti + – bz 2 228 b A 1 g 4 D 6 h 2.43 1.41 0 183 42 323 (43 704) B 1 g 2 D 2 h 2.35, 2.29 1.40, 1.42 6 223 43 807 (44 204) V – bz 2 A 1 g 2 D 6 h 2.22 1.42 0 250 0 A 4 C 1 2.31, 2.22,2.32, 2.82,2.34, 2.26 1.39, 1.44,1.43, 1.40,1.37, 1.45 11, 1,10, 23 228 12 532 A 6 c C 1 2.31, 3.00,3.56, 2.38,2.41, 2.46 1.43, 1.42,1.39, 1.41 1 219 17 843 V + – bz 2 231 b B 1 g 3 D 2 h 2.25, 2.31 1.40, 1.42 6 219 43 675 A 1 g 1 D 6 h 2.21 1.42 0 253 50 851 bz A 1 g 1 D 6 h 1.39 0 a Electronic symmetry species of all states are labeled with the same Cartesian coordinate system used in D 6 h point group. In DFT calculations with GAUSSIAN software the B 1 g symmetry species was incorrectly labeled as B 3 g . b From ZEKE spectra. c Slipped sandwich structure. Table II. Peak positions and assignments for the ZEKE spectra of Ti– and V – bz 2 complexes. s stands for the symmetric metal-benzene stretching mode, t stands for the benzene torsion mode, and b stands for the C–H out-of-plane bending mode. Ti – bz 2 V – bz 2 B 1 g 2 ← A 1 g 1 B 1 g 3 ← A 1 g 2 Position a Assignment Position a Assignment 46 228 Origin 46 655 Origin 46 240 t 0 2 46 885 s 0 1 46 456 s 0 1 47 115 s 0 2 46 470 s 0 1 t 0 2 47 347 s 0 3 46 684 s 0 2 47 576 s 0 4 46 697 s 0 2 t 0 2 46 910 s 0 3 46 921 s 0 3 t 0 2 46 971 b 0 1 47 137 s 0 4 47 149 s 0 4 t 0 2 47 197 b 0 1 s 0 1 47 363 s 0 5 47 377 s 0 5 t 0 2 47 421 b 0 1 s 0 2 47 590 s 0 6 47 601 s 0 6 t 0 2 a The uncertainties in peak positions are ∼ 8 cm − 1 for the Ti – bz 2 B 1 g 2 ← A 1 g 1 transition and ∼ 15 cm − 1 for the V – bz 2 B 1 g 3 ← A 1 g 2 transition. Table III. Electronic transition energies ( T 00 , eV) and vibrational frequencies ( cm − 1 ) of the Ti– and V – bz 2 sandwich complexes from ZEKE spectra and B 3 LYP ∕ 6 - 311 + G ( d , p ) calculations. Ionization energies from previous measurements are listed for the purpose of comparison. ZEKE B3LYP PES PIE Rydberg Ti – bz 2 T 00 B 1 g 2 ← A 1 g 1 5.732(1) 5.48 a 5.5–6.0 b 5.71(2)/5.68(4) c ν s + C 6 H 6 – Ti + – C 6 H 6 stretch 228 223 ν b + C–H out-of-plane bend 741 766 V – bz 2 T 00 B 1 g 3 ← A 1 g 2 5.784(2) 5.46 a 5.95 d 5.75(3) e 6.16(2) f ν s + C 6 H 6 – V + – C 6 H 6 stretch 230 219 a With zero-point vibrational energy corrections. b Reference 6 . c References 4 and 5 . d References 6 and 8 . e References 5 and 7 . f Reference 9 . Table IV. Electronic transitions ( T 00 ) and point groups, ionization energies (IE, eV), M + ∕ M – C distances ({\AA}), symmetric M + – bz 2 stretch frequencies ( ν s + , cm − 1 ), and dissociation energies ( D o and D o + , eV) for M + ∕ M – bz 2 ( M = Sc – Cr ) complexes. IEs and ν s + are from ZEKE spectra, M + ∕ M – C distances from B3LYP calculations, D 0 + from mass spectrometry-based measurements, and D 0 from thermochemical cycles. Sc – bz 2 a Ti – bz 2 V – bz 2 Cr – bz 2 b Transition c A g 1 ← B 1 g 2 A 1 g 3 ← B 1 g 2 B 1 g 2 ← A 1 g 1 B 1 g 3 ← A 1 g 2 A 1 g 2 ← A 1 g 1 Point group D 2 h ← D 2 h D 6 h ← D 2 h D 2 h ← D 6 h D 2 h ← D 6 h D 6 h ← D 6 h IE 5.069 (3) 5.221 (1) 5.732 (1) 5.784 (2) 5.465 (1) M–C 2.44, 2.39 2.44, 2.39 2.27 2.22 2.18 M + – C 2.50, 2.40 2.49 2.35, 2.29 2.25, 2.31 2.19 ν s + 206 201 228 230 264 D o + d 4.2 (2) 5.3 (2) 5.0 (2) 4.2 (2) D o e 2.7 (2) 4.2 (2) 4.0 (2) 2.9 (2)2.8 (2) f a Reference 16 . b Reference 13 . c Electronic symmetry species of all states are labeled with the same Cartesian coordinate system used in D 6 h point group. In DFT calculations with GAUSSIAN software the B 1 g symmetry species was incorrectly labeled as B 3 g . d D o + for M + – bz 2 → M + + 2 bz . D 0 + ( Sc + – bz 2 ) is from Ref. 40 by assuming that the dissociation energy of Sc – bz 2 is twice as that of Sc–bz. D 0 + of the other complexes are from Ref. 39 . e D o = D o + − IE ( M – bz 2 ) − IE ( M ) for M – bz 2 → M + 2 bz . f From threshold photoelectron-photoion coincidence spectroscopy (Ref. 42 ). FIG. 1. PIE spectra of Ti – bz 2 (a) and V – bz 2 (b) complexes seeded in helium carrier. The ionization thresholds are indicated by the vertical arrows. FIG. 2. Experimental ZEKE spectrum in helium carrier (a) and B3LYP simulations ( 150 K ) of spin-allowed transitions of eclipsed Ti – bz 2 [(b)–(d)]. FIG. 3. Relative energies of the electronic states of Ti + ∕ Ti – bz 2 predicted at the B 3 LYP ∕ 6 - 311 + G ( d , p ) level of theory. The spin-allowed transitions [ Δ ( 2 S + 1 ) = ± 1 ] are indicated by the vertical arrows. FIG. 4. Experimental ZEKE spectrum in helium carrier (a) and B3LYP simulations ( 150 K ) of spin-allowed transitions of eclipsed V – bz 2 [(b)–(c)]. ",

year = "2007",

doi = "10.1063/1.2771158",

language = "English",

volume = "127",

number = "11",

}

TY - JOUR

T1 - Electronic states of neutral and cationic bis(benzene) titanium and vanadium sandwich complexes studied by pulsed field ionization electron spectroscopy

AU - Sohnlein, Bradford R.

AU - Lei, Yuxiu

AU - Yang, Dong Sheng

N1 - Funding Information: We gratefully acknowledge financial support from the Experimental Physical Chemistry Program of the National Science Foundation. We also acknowledge additional funding from the Petroleum Research Fund of the American Chemical Society and Kentucky Science and Engineering Foundation. Table I. Electronic states, point groups (PGs), bond lengths ( R , Å), dihedral angle (∠, degrees), symmetric metal-benzene stretches ( ν s + ∕ ν s , cm − 1 ), and relative electronic energies ( E ele , cm − 1 ) of eclipsed Ti– and V – bz 2 sandwich complexes from B 3 LYP ∕ 6 - 311 + G ( d , p ) calculations. The predicted free benzene structure is also given at this level of theory. Electronic energies in parentheses are from CCSD(T) single-point energy calculations. State a PG R M – C R C – C ∠ C – C – C – C ν s + ∕ ν s E ele Ti – bz 2 A 1 g 1 D 6 h 2.27 1.42 0 245 0 B 1 g 3 D 2 h 2.36, 2.31 1.40, 1.43 6 214 2193 (4682) A u 5 D 2 h 2.44, 2.41 1.43, 1.39 3 190 12 744 Ti + – bz 2 228 b A 1 g 4 D 6 h 2.43 1.41 0 183 42 323 (43 704) B 1 g 2 D 2 h 2.35, 2.29 1.40, 1.42 6 223 43 807 (44 204) V – bz 2 A 1 g 2 D 6 h 2.22 1.42 0 250 0 A 4 C 1 2.31, 2.22,2.32, 2.82,2.34, 2.26 1.39, 1.44,1.43, 1.40,1.37, 1.45 11, 1,10, 23 228 12 532 A 6 c C 1 2.31, 3.00,3.56, 2.38,2.41, 2.46 1.43, 1.42,1.39, 1.41 1 219 17 843 V + – bz 2 231 b B 1 g 3 D 2 h 2.25, 2.31 1.40, 1.42 6 219 43 675 A 1 g 1 D 6 h 2.21 1.42 0 253 50 851 bz A 1 g 1 D 6 h 1.39 0 a Electronic symmetry species of all states are labeled with the same Cartesian coordinate system used in D 6 h point group. In DFT calculations with GAUSSIAN software the B 1 g symmetry species was incorrectly labeled as B 3 g . b From ZEKE spectra. c Slipped sandwich structure. Table II. Peak positions and assignments for the ZEKE spectra of Ti– and V – bz 2 complexes. s stands for the symmetric metal-benzene stretching mode, t stands for the benzene torsion mode, and b stands for the C–H out-of-plane bending mode. Ti – bz 2 V – bz 2 B 1 g 2 ← A 1 g 1 B 1 g 3 ← A 1 g 2 Position a Assignment Position a Assignment 46 228 Origin 46 655 Origin 46 240 t 0 2 46 885 s 0 1 46 456 s 0 1 47 115 s 0 2 46 470 s 0 1 t 0 2 47 347 s 0 3 46 684 s 0 2 47 576 s 0 4 46 697 s 0 2 t 0 2 46 910 s 0 3 46 921 s 0 3 t 0 2 46 971 b 0 1 47 137 s 0 4 47 149 s 0 4 t 0 2 47 197 b 0 1 s 0 1 47 363 s 0 5 47 377 s 0 5 t 0 2 47 421 b 0 1 s 0 2 47 590 s 0 6 47 601 s 0 6 t 0 2 a The uncertainties in peak positions are ∼ 8 cm − 1 for the Ti – bz 2 B 1 g 2 ← A 1 g 1 transition and ∼ 15 cm − 1 for the V – bz 2 B 1 g 3 ← A 1 g 2 transition. Table III. Electronic transition energies ( T 00 , eV) and vibrational frequencies ( cm − 1 ) of the Ti– and V – bz 2 sandwich complexes from ZEKE spectra and B 3 LYP ∕ 6 - 311 + G ( d , p ) calculations. Ionization energies from previous measurements are listed for the purpose of comparison. ZEKE B3LYP PES PIE Rydberg Ti – bz 2 T 00 B 1 g 2 ← A 1 g 1 5.732(1) 5.48 a 5.5–6.0 b 5.71(2)/5.68(4) c ν s + C 6 H 6 – Ti + – C 6 H 6 stretch 228 223 ν b + C–H out-of-plane bend 741 766 V – bz 2 T 00 B 1 g 3 ← A 1 g 2 5.784(2) 5.46 a 5.95 d 5.75(3) e 6.16(2) f ν s + C 6 H 6 – V + – C 6 H 6 stretch 230 219 a With zero-point vibrational energy corrections. b Reference 6 . c References 4 and 5 . d References 6 and 8 . e References 5 and 7 . f Reference 9 . Table IV. Electronic transitions ( T 00 ) and point groups, ionization energies (IE, eV), M + ∕ M – C distances (Å), symmetric M + – bz 2 stretch frequencies ( ν s + , cm − 1 ), and dissociation energies ( D o and D o + , eV) for M + ∕ M – bz 2 ( M = Sc – Cr ) complexes. IEs and ν s + are from ZEKE spectra, M + ∕ M – C distances from B3LYP calculations, D 0 + from mass spectrometry-based measurements, and D 0 from thermochemical cycles. Sc – bz 2 a Ti – bz 2 V – bz 2 Cr – bz 2 b Transition c A g 1 ← B 1 g 2 A 1 g 3 ← B 1 g 2 B 1 g 2 ← A 1 g 1 B 1 g 3 ← A 1 g 2 A 1 g 2 ← A 1 g 1 Point group D 2 h ← D 2 h D 6 h ← D 2 h D 2 h ← D 6 h D 2 h ← D 6 h D 6 h ← D 6 h IE 5.069 (3) 5.221 (1) 5.732 (1) 5.784 (2) 5.465 (1) M–C 2.44, 2.39 2.44, 2.39 2.27 2.22 2.18 M + – C 2.50, 2.40 2.49 2.35, 2.29 2.25, 2.31 2.19 ν s + 206 201 228 230 264 D o + d 4.2 (2) 5.3 (2) 5.0 (2) 4.2 (2) D o e 2.7 (2) 4.2 (2) 4.0 (2) 2.9 (2)2.8 (2) f a Reference 16 . b Reference 13 . c Electronic symmetry species of all states are labeled with the same Cartesian coordinate system used in D 6 h point group. In DFT calculations with GAUSSIAN software the B 1 g symmetry species was incorrectly labeled as B 3 g . d D o + for M + – bz 2 → M + + 2 bz . D 0 + ( Sc + – bz 2 ) is from Ref. 40 by assuming that the dissociation energy of Sc – bz 2 is twice as that of Sc–bz. D 0 + of the other complexes are from Ref. 39 . e D o = D o + − IE ( M – bz 2 ) − IE ( M ) for M – bz 2 → M + 2 bz . f From threshold photoelectron-photoion coincidence spectroscopy (Ref. 42 ). FIG. 1. PIE spectra of Ti – bz 2 (a) and V – bz 2 (b) complexes seeded in helium carrier. The ionization thresholds are indicated by the vertical arrows. FIG. 2. Experimental ZEKE spectrum in helium carrier (a) and B3LYP simulations ( 150 K ) of spin-allowed transitions of eclipsed Ti – bz 2 [(b)–(d)]. FIG. 3. Relative energies of the electronic states of Ti + ∕ Ti – bz 2 predicted at the B 3 LYP ∕ 6 - 311 + G ( d , p ) level of theory. The spin-allowed transitions [ Δ ( 2 S + 1 ) = ± 1 ] are indicated by the vertical arrows. FIG. 4. Experimental ZEKE spectrum in helium carrier (a) and B3LYP simulations ( 150 K ) of spin-allowed transitions of eclipsed V – bz 2 [(b)–(c)].

PY - 2007

Y1 - 2007

N2 - Ti- and V- bz2 (bz= C6 H6) sandwich complexes have been prepared in a laser-ablation cluster beam source and studied by pulsed field ionization-zero electron kinetic energy photoelectron spectroscopy and theoretical calculations. The ground electronic states of the neutral Ti- and V- bz2 complexes are determined to be A 1g 1 and A 1g 2, and their ionization energies are measured to be 5.732±0.001 and 5.784±0.002 eV, respectively. These neutral complexes have 6 binding and are in an eclipsed D6h configuration with flat benzene rings. Ionization of the A 1g 1 and A 1g 2 neutral states of Ti- and V- bz2 yields the B 1g 2 and B 1g 3 ion states, respectively, in a D2h point group with slightly puckered benzene rings. In addition, the binding and structures of these two complexes are compared with other first-row transition metal bis(benzene) sandwiches.

AB - Ti- and V- bz2 (bz= C6 H6) sandwich complexes have been prepared in a laser-ablation cluster beam source and studied by pulsed field ionization-zero electron kinetic energy photoelectron spectroscopy and theoretical calculations. The ground electronic states of the neutral Ti- and V- bz2 complexes are determined to be A 1g 1 and A 1g 2, and their ionization energies are measured to be 5.732±0.001 and 5.784±0.002 eV, respectively. These neutral complexes have 6 binding and are in an eclipsed D6h configuration with flat benzene rings. Ionization of the A 1g 1 and A 1g 2 neutral states of Ti- and V- bz2 yields the B 1g 2 and B 1g 3 ion states, respectively, in a D2h point group with slightly puckered benzene rings. In addition, the binding and structures of these two complexes are compared with other first-row transition metal bis(benzene) sandwiches.

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U2 - 10.1063/1.2771158

DO - 10.1063/1.2771158

M3 - Article

AN - SCOPUS:34648843507

VL - 127

IS - 11

M1 - 114302

ER -

Electronic states of neutral and cationic bis(benzene) titanium and vanadium sandwich complexes studied by pulsed field ionization electron spectroscopy

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