6

61 611 Democritus 5 atom

18 19 1805 J. Dalton :

Dalton

19 20 18

1879 W.Crookes 1897 J. J. Thomson em = 1.7588108 Cg-1 1909 R. A. Millikan 1.60210-19 C m = 9.1110-28 g

19 1895 W. C. Rongen XXX- 1896 A. H. Becquerel M. S. Curie

1911 Rutherford G. J. Mosley 1913

1886 E. Goldstein 1920 1932 J. Chadwick

612 61 61

HHHH 62 62

1883 Balmer HHHH B n 3456 61 Balmer 61

1913 Rydberg 62 Rydberg 1 cmRH 1.097105 cm-1n1 n2 n2 n1 Lyman Paschen Bracket Rydberg 62

Rutherford 1913 Bohr

613 1900 Planck Planck 1905 Einstein Einstein

E = h 63 E h Planck 6.62610-34 Js

Bohr EBohr eV 1 1.602 10-19 C 1 V 1.602 10-19 J 1913 Bohr Planck Einstein Rutherford Bohr 64

n 123 64n = 1 E1 = 13.6 eV

n = 2 E2 = 13.6/4 eV

n = 3 E3 = 13.6/9 eV n n E = 0

Bohr h = E2 E1 v = (E2 - E1) / h 65

E2 E1 h Planck (64) (65) 6662Rydberg 66

Rydberg Planck

62 621 17 Newton Huygens 20

(63) E = h E = mc2 mc2 = h 67

P P = m c (68) (68) (67)

P = hv / c P = h / (69) (69) P (69)

1924 Louis de Broglie h P m v = h / P = h / mv (610)

1927 C. J. Davisson L. H. Germer

622 x t x = F( t ) v t v = f( t ) P

1927 W. Heisenberg x P h / 2 611 x v h / 2m 612 x P v

(611) h/2 x P 612 h/2m m x P h / 2 611 x v h / 2m 612

m = 0.01 kg h/2m 10-32 x 10-9 m v 10-23 ms-1 m = 9.11 10-31 kg, h/2m 104 1010 m x 10-12 m v 108 ms-1

623

Davisson Germer

1926 E. Schrdinger Schrdinger Schrodinger

63 631 Schrdinger Schrdinger 613

xyz E Schrodinger E V m Schrdinger h Planck

Schrdinger

Schrdinger Schrdinger V V

r V Schrdinger (613)

z 63

r 65 r P 0 OP z 0 OP xOy OP x 0 2

x = r sin cos y = r sin sin z = r cos Schrdinger

614 r

r ( 615 )( 616 ) ( 617 )

( ) R ( r ) ( ) nl mm = 0 1 2 , ...l = 012, ..., l m n n 1 l R ( r ) ( ) ( )

( r ) = R ( r ) ( ) ( ) 618

Y ( ) = ( ) ( ) 619618 ( r) = R ( r )Y ( ) 620 R ( r ) Y ( ) 621

r nlm n = 1 l = 0 m = 0 :

n = 2 l = 0 m = 0

622

n = 2 l = 1 m = 0

624 Z a0 Bohr 623 n = 3 l = 2 m = 1

nlm ( r ) n,l,m orbital (orbit) 1,0,0 1s 1s 2,0,0 2s 2s2,1,0 2pz 2pz

2px2py2,1,12,1,-1

Schrdinger ( r ) ( r ) n, l, m E (625) He+Li2+ (626) n Z

nlm ( r ) nlm 6 -3 -2 nlm nlm

n 123 KLMNOP n E n En E n E 0 n 1 n

n n = 1n = 2n = 3n

2 l l 01234 n1 spdfg l n 0 n1 n M l 627

l E n l n l N l l E E 4 s E 4 p E 4 d E 4 f E l n E ns = E np = E nd = E nf

l n = 4 l 4 012 34 l = 0 s 4s l = 1 p 4p l = 2 d 4d l = 3 f 4f 4 n 4 l

3 m m 0 1 2 3 l m l 0 l, m 2 l + 1 M M z Mz m (628)

M z Mz l = 1626 m = 0m = +1m =1 M z Mz 0h/2h/2

z O 64 m = 1 M z h/2 M OA z 64 M

M z m = 1 OC z = 135m = 0 OB z = 90

m l = 0 m 0 s l = 1m 01 1 p x y z

m p x y z p p p 3 l = 2m 01122 d d l = 3 f f 7

nlm n = 1l = 0m = 0 2s n = 3l = 2m = 1 3d

4 ms Bohr

2p 1s Bohr nlm 2p 1s (629) 1925 Uhlenbeck Goldchmidt Ms ms

ms ms = 1/2 ms nlm nlmms

633 1

( r ) ( r ) ( r )2Pr

1s 65 65 1s

65 1s 65 2

22 66 66

66 s p d

2 1s 67 1s 68 1s

67 1s 68 1s 67 1s 95%1s 68

2 r1s2 r 69 69 1s

634 r 626 ( r, , ) = R ( r ) Y ( , ) r

1 r r 610 r 4r2 4r2r24r22r4r22r r4r22 610

D ( r ) = 4r22 630D ( r ) r630 D ( r ) r 611

611

D ( r ) 4r2 22 r D ( r ) r 2 D ( r ) D ( r ) 1s r = r0 = 53 pm D ( r ) 53 pm 1s r0 Bohr

2s 3s ns n2p 3p np n13d 4d nd n2 N n l N nl (631)

1 n 2s 2p 1s 3s3p3d 2s 2p 4s4p4d 4f

N N nl1 (632)

612 210

2 ( r) = R ( r )Y ( ) 620 Y ( ) Y2 66

2,1,0 (623) Y ( ) cos Y cos 61 61 Ycos 0 15 30 45 60 90 120 135 150 165 180Ycos 1.0 0.97 0.87 0.71 0.50 0 -0.50 -0.71 -0.87 -0.97 -1.0

z Y cos 612a

z 360 612b 2,1,0 xOy + Y

spd 613 () +

613

64 641 n l l E E 4s E 4p E 4d E 4f n l E n E 3d > E 4s

626

Z Z* Z* = Z (633)

(634) Slater 62

62

1s2s2p3s3p3d4s4p4d4f5s5p1s0.302s2p0.850.353s3p1.000.850.353d1.001.001.000.354s4p1.001.000.850.850.354d1.001.001.001.001.000.354f1.001.001.001.001.001.000.355s5p1.001.001.001.000.850.850.850.35

61 Ti 3p 3d E3p E3d Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2 3p =0.35 7+0.85 8+1.00 2= 11.253d =0.35 1+1.00 18= 18.35 3p 3d E3p = 174.63 eVE3d = 20.13 eV

62 61 3d 4s 0.85 3d 0.35 3p 4s 0.85 3d 1.00

4s 3d 4s 3d 614 4s 3d

62 K 4s 3d 4s K 1s2 2s2 2p6 3s2 3p6 4s14s 4s =0.85 8+1.00 10= 16.8E4s 4.11 eV

3d K 1s2 2s2 2p6 3s2 3p6 3d13d 3d = 1.00 18 = 18E3d = 1.51 eV

E4s < E3d K 4s Enf End Enp Ens E4s < E3d

642 1 Pauling Pauling 615 ()

615 Pauling

Pauling 7 615

1s 1s 615 2s 2p 2s 615 2p p 615

3s 3p3s 3p p

4s3d 4p4s 3d d 4p p

5s4d 5p5s 4d d 5p p

6s4f5d 6p6s 4f f5d d 6p p

7s5f6d 7p7s 5f f 6d d 7p p ns np

n + 0.7 l n + 0.7 l 7 p n + 0.7 l = 7 + 0.7 1 = 7.76 d n + 0.7 l = 6 + 0.7 2 = 7.45 f n + 0.7 l = 5 + 0.7 3 = 7.17 s n + 0.7 l = 7 + 0.7 0 = 7.0E7s E5f E6d E7p n + 0.7 l

2Pauling Pauling F. A. Cotton Cotton 616

616 Cotton

1 H n l E ns < E np < E nd < E nf

1520 E4s E3d 21 E3d E4s

643 Pauli Hund

1 (1)

(2) Pauli 1925 W. Pauli Pauli Pauli

Pauli 1 ms ms = 1/2 2 n l 01234 (n1) n l m 13579, (2 n1) n 13579 (2n1)n2 Pauli 2n2

(3) Hund F. Hund 6 Pauli 1s 2 2s 2 2 2p 1s2 2s2 2p2

Hund 2p 617 617

Hund p6d10f14 p3d5 f7 p0d0 f0

2 Z = 11 1s2 2s2 2p6 3s1 Z = 19 1s2 2s2 2p6 3s2 3p6 4s1 [Ar] 4s1

24 [Ar] 3d54s1 [Ar] 3d4 4s2 3d5 [Ar] 3d10 4s1 [Ar] 3d9 4s2 3d 4s 4s 3d 63

63

1HHydrogen1s12HeHelium1s23LiLithium[He] 2s14BeBeryllium[He] 2s25BBoron[He] 2s22p16CCarbon[He] 2s22p27NNitrogen[He] 2s22p38OOxygen[He] 2s22p49FFluorine[He] 2s22p510NeNeon[He] 2s22p6

11NaSodium[Ne] 3s112MgMagnesium[Ne] 3s213AlAluminum[Ne] 3s23p114SiSilicon[Ne] 3s23p215PPhosphorus[Ne] 3s23p316SSulfur[Ne] 3s23p417ClChlorine[Ne] 3s23p518ArArgon[Ne] 3s23p619KPotassium[Ar] 4s120CaCalcium[Ar] 4s2

21ScScandium[Ar] 3d14s222TiTitanium[Ar] 3d24s223VVanadium[Ar] 3d34s224CrChromium[Ar] 3d54s125MnManganese[Ar] 3d54s226FeIron[Ar] 3d64s227CoCobalt[Ar] 3d74s228NiNickel[Ar] 3d84s229CuCopper[Ar] 3d104s130ZnZinc[Ar] 3d104s2

31GaGallium[Ar] 3d104s24p132GeGermanium[Ar] 3d104s24p233AsArsenic[Ar] 3d104s24p334SeSelenium[Ar] 3d104s24p435BrBromine[Ar] 3d104s24p536KrKrypton[Ar] 3d104s24p637RbRubidium[Kr] 5s138SrStrontium[Kr] 5s239YYttrium[Kr] 4d15s240ZrZirconium[Kr] 4d25s2

41NbNiobium[Kr] 4d45s142MoMolybdenum[Kr] 4d55s143TcTechnetium[Kr] 4d55s244RuRuthenium[Kr] 4d75s145RhRhodium[Kr] 4d85s146PdPalladium[Kr] 4d1047AgSilver[Kr] 4d105s148CdCadmium[Kr] 4d105s249InIndium[Kr] 4d105s25p150SnTin[Kr] 4d105s25p2

51SbAntimony[Kr] 4d105s25p352TeTellurium[Kr] 4d105s25p453IIodine[Kr] 4d105s25p554XeXenon[Kr] 4d105s25p655CsCesium[Xe] 6s156BaBarium[Xe] 6s257LaLanthanum[Xe] 5d16s258CeCerium[Xe] 4f15d16s259PrPraseodymium[Xe] 4f36s260NdNeodymium[Xe] 4f46s2

61PmPromethium[Xe] 4f56s262SmSamarium[Xe] 4f66s263EuEuropium[Xe] 4f76s264GdGadolinium[Xe] 4f75d16s265TbTerbium[Xe] 4f96s266DyDysprosium[Xe] 4f106s267HoHolmium[Xe] 4f116s268ErErbium[Xe] 4f126s269TmThulium[Xe] 4f136s270YbYtterbium[Xe] 4f146s2

71LuLutetium[Xe] 4f145d16s272HfHafnium[Xe] 4f145d26s273TaTantalum[Xe] 4f145d36s274WTungsten[Xe] 4f145d46s275ReRhenium[Xe] 4f145d56s276OsOsmium[Xe] 4f145d66s277IrIridium[Xe] 4f145d76s278PtPlatinum[Xe] 4f145d96s179AuGold[Xe] 4f145d106s180HgMercury[Xe] 4f145d106s2

81TlThallium[Xe] 4f145d106s26p182PbLead[Xe] 4f145d106s26p283BiBismuth[Xe] 4f145d106s26p384PoPolonium[Xe] 4f145d106s26p485AtAstatine[Xe] 4f145d106s26p586RnRadon[Xe] 4f145d106s26p687FrTrancium[Rn] 7s188RaRadium[Rn] 7s289AcActinium[Rn] 6d17s290ThThorium[Rn] 6d27s2

91PaProtactinium[Rn] 5f26d17s292UUranium[Rn] 5f36d17s293NpNeptunium[Rn] 5f46d17s294PuPlutonium[Rn] 5f67s295AmAmericium[Rn] 5f77s296CmCurium[Rn] 5f76d17s297BkBerkelium[Rn] 5f97s2198CfCalifornium[Rn] 5f107s299EsEinsteinium[Rn] 5f117s2100FmFermium[Rn] 5f127s2101MdMendelevium[Rn] 5f137s2

102NoNobelium[Rn] 5f147s2103LrLawrencium[Rn] 5f146d17s2104RfRutherfordium[Rn] 5f146d27s2105DuDubnium[Rn] 5f146d37s2106SgSeaborgium[Rn] 5f146d47s2107BhBohrium[Rn] 5f146d57s2108HsHassium[Rn] 5f146d67s2109MtMeitnerium[Rn] 5f146d77s2110DsDarmstadtium[Rn] 5f146d87s2111Uuu111Unununium[Rn] 5f146d97s2112Uub112Ununbiium[Rn] 5f146d107s2

65 1869 D. I.Mendeleev 63 64 A. Werner

64

651 n 1s 1s 2

8 ns np 8 18 ns(n1)d np 18 32 6s4f5d 6p 32

32 87 118 7s5f6d 7p 32 2003 8 116 Sn [Kr] 4d105s25p2 5p Sn

65

1 1 1 1 2 2 2 2 4 8 3 3 2 4 8 4 4 3 9 18 5 5 3 9 18 6 6 4 16 32 7 7 4 16 32

652 18 A 64 1213141516 17 A IA VIIA ns np B 3456711 12 B IB VIIB( n1)d

IIIB VIII 89 10 ( n1)d 8 10 ( n1)d 6-10 ns0-2

653 5 66

66

s s IAIIA ns1~2p p IIIAIVA VA VIA VIIA 0 VIII A ns2 np1~6s p s p 8 0 s p

d (n1)d IIIB IVB VB VIB VIIB VIII (n1)d1~10ns0~2 (n1) d 456 d d ( n1)d ns 8 VIII

ds ( n1 )d10ns1~2 d 12 s d ds IB IIB p d Ds ns ds f f (n 2)f0~14 (n1)d0~2 ns2 (n2)f

66

661 1

11

2 ab

Li Be B C N O F Ner/pm 152 113 86 72

Na Mg Al Si P S Cl Ar r/pm 186 160 143 118 108 106

d10 f7 f14

Sc Ti V Cr Mn Fe Co Ni Cu Zn r/pm 162 147 134 128 127 126 125 124 128 134

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd r/pm 180 160 146 139 136 134 134 137 144 149CuZn PdAgCd d10

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

r/pm 183 182 182 181 183 180 208 180 177 176 176 176 176 194 174Eu Yb f7 f14

La Lu 10 pm

15 10 pm Zr HfNb TaMo W

K Ca Sc Ti V Cr Mn Fe Corpm 232 197 162 147 134 128 127 126

Rb Sr Y Zr Nb Mo Tc Rurpm 248 215 180 160 146 139 136 134

Cs Ba La Hf Ta W Re Or rpm 265 217 183 159 146 139 137 135

rpm rpm rpm Li 152 Be 113 B 86Na 186 Mg 160 Al 143 K 232 Ca 197 Ga 135 Rb 248 Sr 215 In 167Cs 265 Ba 217 Tl 170

662 I1

I1 13

Li Be B C N O F NeI1/kJmol-1 520 900 801 1086 1402 1314 1681 2081

Na Mg Al Si P S Cl ArI1/kJmol-1 496 738 578 787 1012 1000 1251 1521

O S p p N P Sc Ti V Cr Mn Fe Co Ni Cu ZnI1/kJmol-1 633 659 651 653 717 762 760 737 746 906

Mn Zn 3d5 4s2 3d10 4s2 (n1)d (n2)f

I1 / kJmol1 I1 / kJmol1 Li 520 Be 900 Na 496 Mg 738 K 419 Ca 590 Rb 403 Sr 550 Cs 376 Ba 503

Y Zr Nb Mo Tc Ru Rh Pd Ag CdI1/kJmol-1 600 640 652 684 702 710 720 804 731 868 La Hf Ta W Re Os Ir Pt Au HgI1/kJmol-1 538 659 728 759 756 814 865 864 890 1007

8 I1 I2 I3 Z* r 67

67 InkJmol-1 I1 I2 I 3 I4 I 5

1 H 1312 2 He 2372 5250 3 Li 520 7298 11815 4 Be 900 1757 14849 21007 5 B 801 2427 3660 25026 32827

520 kJmol-1 7298 kJmol-1 + 1 900 kJmol-1 1757 kJmol-1 14849 kJmol-1 + 2 67

E E1 E2 E3 663

E1 14

Li Be B C N O F Ne

E1kJmol-1 59.6 26.7 121.9 141.0 328.2

Na Mg Al Si P S Cl Ar

E1kJmol-1 52.9 42.6 133.6 72.0 200.4 348.6

E1 VIA VIIA E1 / kJmol1 E1 / kJmol1

O 141.0 F 328.2 S 200.4 Cl 348.6 Se 195.0 Br 324.5 Te 190.2 I 295.2

VIA VII1A

Cl2 H2 664

1932 Pauling Pauling F 4.0 F 4.0 Pauling 1934 Millikan I E = (I + E) (635) Millikan

m n p s p s p s Pauling eV s 1989 L. C. Allen (636)

s Pauling p Li Be B C N O F Ne p 0.98 1.57 2.04 2.55 3.04 3.44 3.98 s 0.91 1.58 2.05 2.54 3.07 3.61 4.19 4.79

Na Mg Al Si P S Cl Ar p 0.93 1.31 1.61 1.91 2.19 2.58 3.16 s 0.87 1.29 1.61 1.92 2.25 2.59 2.87 3.24

2.0 2.0 p s p s

Li 0.98 0.91 F 3.98 4.19 Na 0.93 0.87 Cl 3.16 2.87 K 0.82 0.73 Br 2.96 2.69 Rb 0.82 0.71 I 2.66 2.36 Cs 0.79