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Thermodynamic and electronic properties for lanthanide cations

Ln⁺ ground	Ln⁺ state valence configuration	Ln⁺ term symbol	Promotion energy^a to 5d¹ 6s¹	IE(Ln)^b (eV)	IE(LnO)^b (eV)	OA(Ln⁺)^c(kcal mol^-1)	SA(Ln⁺)(kcal mol^-1)

La⁺	5d²	³F₂	4.5±3.0	5.58	4.90	206.6±3.4	124.4±2.4^e
Ce⁺	4f¹5d²	⁴H_7/2⁰	4.6±5.7	5.54	4.90	203.6±5.9	125±14^d
Pr⁺	4f³6s¹	(9/2,1/2)_4⁰	22.3±0.8	5.47	4.90	189.6±4.3	—
Nd⁺	4f⁴6s¹	⁶I_7/2	34.8±8.3	5.53	4.97	180.8±4.3	—
Pm⁺	4f⁵6s¹	⁷H₂⁰	46.4±7.2	5.58	—	—	—
Sm⁺	4f⁶6s¹	⁸F_7/2	62.1±5.8	5.64	5.55	139.6±4.3	—
Eu⁺	4f⁷6s¹	⁹S₄⁰	92.8±5.0	5.67	6.48	93.2±4.3	59±7^d
Gd⁺	4f⁷5d¹6s¹	¹⁰D_5/2⁰	0.0	6.15	5.75	180.0±4.3	106.2±13.8^d
Tb⁺	4f⁹6s¹	(15/2,1/2)₈⁰	9.3±8.1	5.86	5.62	171.0±5.9	—
Dy⁺	4f¹⁰6s¹	(8,1/2)_17/2	36.0±6.1	5.94	6.08	143.4±5.9	—
Ho⁺	4f¹¹6s¹	(15/2,1/2)₈⁰	37.8±5.4	6.02	6.17	141.3±4.3	—
Er⁺	4f¹²6s¹	(6,1/2)_13/2	34.5±3.1	6.11	6.30	140.3±4.3	—
Tm⁺	4f¹³6s¹	(7/2,1/2)₄⁰	55.5±7.4	6.18	6.44	116.6±4.3	—
Yb⁺	4f¹⁴6s¹	²S_1/2	79.4±4.0	6.25	6.55	88.1±5.9	59.0±0.1^e
Lu⁺	4f¹³6s²	¹S₀	36.6±3.6	5.43	6.79	128.0±4.3	107.2±0.1^e

^a In kcal mol^-1 from Reference [1] with the correct value for Tm⁺ which had been wrongly assigned in Reference [1].
^b From Refernce [2]. The error on all numbers is quoted as ±0.1eV.
^c Based on values for ΔH°_f(LnO), ΔH°_f(Ln), ΔH°_f(O), IE(Ln) and IE(LnO) found in Reference[2].
^d XA (X=O, S) values were taken on the basis of °H_fo (LnX⁺) °H_fo (Ln⁺), °H_fo (X), found in Reference [3].
^e SA values were taken on the basis of °H_fo (Ln⁺), °Hfo (S) found in ref.31, and IE(LnS) and D(Ln-S) found in Reference [4].

Thermodynamic and electronic properties for atomic cations

M⁺	SA(M⁺)^a	IE(M)^b	M⁺	SA(M⁺)^a	IE(M)^b	M⁺	SA(M⁺)	IE(M)^b

K⁺	—	4.34	Rb⁺	—	4.18	Cs⁺	—	3.89
Ca⁺	—	6.11	Sr⁺	—	5.69	Ba⁺	—	5.21
Sc⁺	114.6±1.2	6.56	Y⁺	126.6±1.9	6.22	La⁺	124±12^d	5.58
Ti⁺	109.3±1.7	6.83	Zr⁺	127.3±5.0	6.63	Hf⁺	—	6.83
V⁺	87.2±2.4	6.75	Nb⁺	127.1±2.4	6.76	Ta⁺	—	7.55
Cr⁺	61.9±3.8	6.77	Mo⁺	84.8±1.2	7.09	W⁺	—	7.86
Mn⁺	58.0±5.5	7.43	Tc⁺	—		Re⁺	—	7.83
Fe⁺	70.9±1.0	7.90	Ru⁺	68.8±1.4	7.36	Os⁺	—	8.43
Co⁺	68.1±2.1	7.88	Rh⁺	54.0±3.1	7.46	Ir⁺	—	8.97
Ni⁺	56.6±0.96	7.64	Pd⁺	47.1±1.4	8.34	Pt⁺	—	8.96
Cu⁺	47.8.4±3.3	7.72	Ag⁺	29.4±3.1	7.58	Au⁺	—	9.23
Zn⁺	47.3±2.9	9.39	Cd⁺	—	8.99	Hg+	—	10.44
Ga⁺	—	6.00	In⁺	40±12^c	5.79	Tl⁺	—	6.11
Ge⁺	86±14^c	7.90	Sn⁺	77c	7.34	Pb⁺	55±12^c	7.42
As⁺	—	9.79	Sb⁺	—	8.61	Bi⁺	48±12^c	7.29
Se⁺	102±5^c	9.75	Te⁺	—	9.01

^a Unless indicated otherwise, values for SA(M⁺) are taken from the review of P. B. Armentrout. (Reference [7])
^b Taken from Reference [5].
^c Determined from °H_fo (MS⁺), °H_fo (M⁺), and °H_fo (S) found in Reference [6].
^d Determined from IE(La) found in Reference [5] and from IE(LaS) and D(La-S) found in Reference [8].

Table 2. O-atom affinities, D0(M⁺-O) in kcal mol^-1, and ionization energies, IE(M) in eV, for the metal ions taken, with few exceptions, from the review by Schröder et al.²³

First Row			Second Row			Third Row

M⁺	OA(M⁺)	IE(M)	M⁺	OA(M⁺)	IE(M)	M⁺	OA(M⁺)	IE(M)

K⁺	3	4.34	Rb⁺	7	4.18	Cs⁺	14	3.89
Ca⁺	77.2	6.11	Sr⁺	71.4	5.70	Ba⁺	92.8	5.21
Sc⁺	164.6±1.4^a	6.56	Y⁺	167.0±4.2^b	6.22	La⁺	206±4^d	5.58
Ti⁺	158.6±1.6^a	6.83	Zr⁺	178.9±2.5^b	6.63	Hf⁺	173±5^e	6.83
V⁺	134.9±3.5^a	6.75	Nb⁺	164.4±2.5^b	6.76	Ta⁺	188±15^e	7.55
Cr⁺	85.8±2.8^a	6.77	Mo⁺	116.7±0.5^b	7.09	W⁺	166±10^f	7.86
Mn⁺	68.0±3.0^a	7.43	Tc⁺	—		Re⁺	115±15^g	7.83
Fe⁺	80.0±1.4^a	7.90	Ru⁺	87.9±1.2^c	7.36	Os⁺	100±12^h	8.44
Co⁺	74.9±1.2^a	7.88	Rh⁺	69.6±1.4^c	7.46	Ir⁺	59^e	8.97
Ni⁺	63.2±1.2^a	7.64	Pd⁺	33.7±2.5^c	8.34	Pt⁺	77I, 75±2^j	8.96
Cu⁺	37.4±3.5^a	7.72	Ag⁺	28.4±1.2^c	7.58	Au⁺	—	9.23
Zn⁺	38.5±1.2^a	9.39	Cd⁺	—	8.99	Hg+	—	10.44
Ga⁺	5.6	6.00	In⁺	—	5.79	Tl⁺	—	6.11
Ge⁺	81.8	7.90	Sn⁺	75.1	7.34	Pb⁺	53.2	7.42
As⁺	147±2^k	9.81	Sb⁺	—	8.64	Bi⁺	41.6	7.29
Se⁺	92^k	9.75	Te⁺	96.6	9.01

^a Reference [9]	^b Reference [10]	^c Reference [11]	^d Reference [12]	^e Reference [13]	^f Reference [14]
^g Reference [15]	^h Reference [16]	ⁱ Reference [17]	^j Reference [18]	^k Reference [19]

References
[1] G.K. Koyanagi, D.K. Bohme, J.Phys. Chem. A 105 (2001) 8964.

[2] S.G. Lias, J.E. Bartmess, J.F. Liebman, J.L. Liebman, J.L. Holmes, R.D. Levin, W.G. Mallard, J. Phys. Chem. Ref. Data 17 (suppl. 1) (1988).

[3] Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data, Supplement (1988), 17, 861 pp.

[4] Luo, Y.; Wan, X.; Ito, Y.; Takami, S.; Kubo, M.; Miyamoto, A. Chem. Phys. (2002), 282, 197.

[5] Lide, D. R. CRC Handbook of Chemistry and Physics, 82^nd Edition, (2001).

[6] Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Journal of Physical and Chemical Reference Data, Supplement (1988), 17, 861.

[7] Armentrout, P. B. Int. J. Mass Spectrom. (2003), 227, 289.

[8] Luo, Y.; Wan, X.; Ito, Y.; Takami, S.; Kubo, M.; Miyamoto, A. Chem. Phys. (2002), 282, 197.

[9] Freiser, B. S. (ed) (1996) Organnometallic ion chemistry. Kluwer, Dordrecht.

[10] Sievers, M. R.; Chen, Y.-M.; Armentrout, P. B. J. Chem. Phys. 1996, 105, 6322.

[11] Chen, Y.-M.; Armentrout, P .B. J. Chem. Phys. 1995, 103, 618.

[12] Clemmer, D. E.; Dalleska, N. F.; Armentrout, P. B. Chem. Phys. Lett. 1992, 190, 259.

[13] Lias, S. G; Bartmess, J. E; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17: Suppl 1 [14] Blagojevic, V.; Lavrov, V.V.; Orlova, G.; Bohme, D.K. Chem. Phys. Lett. 2004, 389, 303.

[15] Beyer, M. (1996) Dissertation, Technical University München.

[16] Irikura, K. K.; Beauchamp, J. L. J. Am. Chem. Soc. 1989, 111, 75.

[17] Pavlov, M.; Blomberg, M. R. A.; Siegbahn, P. E. M.; Wesendrup, R.; Heinemann, C.; Schwarz, H. J. Phys. Chem. A 1997, 101, 1567.

[18] Zhang, X.-G.; Armentrout, P. B. J. Phys. Chem. A 2003, 107, 8904.

[19] S. Petrie, private communications. The calculations were done using the QCISD(T)/6-311+G(3df) method; the value for OA(Se⁺) does not include a spin-orbit correction.

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