2P120ÁÞÀh­3ÐLNAG5E

ÏÌ{|ï¥þÔú 1Ākò½ 2Āò 3Ā¡×ê 4ĀRTzó¤ù 5ÿïà ô 1Āìw ³s 2Āpá ]i 3Ā e 4ĀýÕ ré 5  cÙÉ@ID684ÙÉ°¿ç+ëm3v)cË/ÁÞÀh­3ÐÙÉ

""Ö210-Þh­3Ðî¿1|ï¥!1%~£Z1©19K Uð03}x!LNAG5E– 54Xe

ÏÌ{|ï¥îø¥

ÏÌ{|ï¥cÅÚÞVî¿}x019K

h­3ÐX.1=7FLM{}x10=7FLM{ÏÌï¥!|ï¥~0

±¹ªèjëªèj:DY,|ï¥3£Z0*?;JND{ Ù É § ·  Î ­  ÁÞÙÉ!¯j£y10©}x-

|ï¥3X+µãÀ

ÏÌ|ï¥¨Ê^Û10d¹

0O§?;JND{!<NH:Do/üÊ30*âæ¢¥ÏÌ\¥CM.Áî¿!2P105 ß¸}x0! LNAG5Eï!ÁÞ
0qÑm!ÁÞ3v)ÙÉ!ÁÞ3ÐX1|ï¥3Y

Ø²

íjÙÉ¨Ø0¬ÂÇ!Ā-/<NHÏÌ96>{|ï¥3î¿/m®

o/ca¥ï+Î­!

KKCM3Y÷!3ÃÜ¬ÂÇ!R [2] -0 3

Douglas-Kroll (DK3) åW-ÁÞÀh­3o/ä(96>{«ñ®KCM3Yîø¥!S ` Ù É 3 Ö    57La ! (943333/8433/743) (943333/8433/743/7)´/! TableāSCF ÙÉ!

m! (943333/8433/74/7) Î­ýÕ [3] -0 B-spline |ï¥ÄX|ï¥!B-splinec

58Ce  64Gd  71Lu

Î­Q#1.

Î­3 0.14 – 0.30 hartree Æ !E 3Ýb¼0

B> DÙÉ  57LaO  57LaF cSCF ÙÉ CCSD(T) (coupled-cluster singles anddoubles with non-iterative triples correction) ÙÉ3Öca¥3¶*57La (943333/8433/743)
5p  6s ÏÌï¥311 (21) cfDZP ¾m[|ï¥TZP  QZP ¾5sm[|ï¥! 5s  5p 3 (21) 6s 3 (111)cf1.3õÁï¾| [4] NOSeC-V-DZP(0/21/31/22)NOSeC-V-QZP (0/21/31/22/3)NOSeC-V-TZP (0/21/31/32/11/1) Í(t2'57La|º

4f âæ!öl«âæ04f 0|ï¥+g

O  F|ï¥!0 TK/NOSeC-V-DZPTK/NOSeC-V-TZPTK/NOSeC-V-QZP [1] 3Y¾ÙÉÎ­3 Table 2Ä|ï¥0ûOÒ!Ó0'

NOSeC-V-QZP !Cao È [5] µ$ h ï¥!O_~ s<NH:D|ï¥0Î­3P

Cao È%&uÈnÐ¦»[1] http://setani.sci.hokudai.ac.jp/sapporo/[2] Nakajima, T.; Hirao, K. J Chem Phys 2000, 113, 7786.
[3] Saito, L. S. J Chem Phys 2009, 130, 074306.
[4] Sekiya, M.; Noro, T.; Koga, T.; Saito, L. S. J Comput Chem, in press.
[5] Cao, X.; Dolg, M. J Chem Phys 2001, 115, 7348.

. g '0ï¥!11O_Table 1. DK3 SCF energies and errors relative to the B-spline SCF energies in hartree.
SCF Energy

AtomConfiguration
2

158Ce

2

1[Xe]6s 4f 5d

59Pr

2

3242

52

62

764Gd

2

7[Xe]6s 4f 5d

65Tb

2

92

1067Ho2[Xe]6s 4f

1168Er[Xe]6s24f 1257La[Xe]6s 5d[Xe]6s 4f

60Nd[Xe]6s 4f

61Pm[Xe]6s 4f

62Sm[Xe]6s 4f

63Eu[Xe]6s 4f[Xe]6s 4f

66Dy[Xe]6s 4f

69Tm

213214214[Xe]6s 4f70Yb[Xe]6s 4f

71Lu

1

1

[Xe]6s 4f 5d1



Present

B-spline!E–8489.258510–8489.398628

0.140118–8856.322491–8856.470752

0.148261–9233.065740–9233.223828

0.158088–9619.658363–9619.825306

0.166943–10016.18225–10016.35875

0.17650–10422.80405–10422.98978

0.18573–10839.71275–10839.90883

0.19608–11266.89099–11267.09554

0.20455–11704.28084–11704.49948

0.21864–12152.51893–12152.74959

0.23066–12611.54339–12611.78717

0.24378–13081.47168–13081.72826

0.25658–13562.55377–13562.82458

0.27081–14054.93591–14055.22080

0.28489–14558.73920–14559.03503

0.29583

Table 2. Comparison of bond lengths (Re), vibrational frequencies (!e), and dissociation energies (De).

SCF

CCSD(T)bSCF

CCSD(T)b

CCSD(T)bNOSeC-V-DZP

1.821

1.867

888

800

7.39

NOSeC-V-TZP

1.811

1.847

891

819

7.89

NOSeC-V-QZP

1.805

1.837

884819

8.24

c

1.806

1.836

8648148.30

813(8.23)

LaO( 2! +)

Cao and Dolg
Exptl.
LaFd

1.826

1 +(!)
NOSeC-V-DZP

2.066

2.052

590

604

6.50

NOSeC-V-TZP

2.059

2.041

566

582

6.69

NOSeC-V-QZP

2.052

2.031

567

584

6.93

c

2.044

2.027

567

578

6.92

570

(6.81)

Cao and Dolg
Exptl.
aDe (D0)a / eV!e /cm-1

Re / Åd

2.027

D0 values are given in the parentheses.
Inactive orbitals in the CCSD(T) calculations are 1s-4s, 2p-4p, 3d for La, and 1s for O and F.
cSee [5].
dHuber, K. P.; Herzberg, G. In Molecular Spectra and Molecular Structure IV. Constants of Diatomic Molecules;
Van Nostrand Reinhold: New York, 1979.
b