Relativistic Effects in Chemistry, Applications

by Balasubramanian, Krishnan

• ISBN13: 9780471179917
• ISBN10: 0471179914
• Edition: 1st
• Format: Hardcover
• Copyright: 1997-05-23
• Publisher: Wiley-Interscience

Summary

E = mc2 and the Periodic Table . . . RELATIVISTIC EFFECTS IN CHEMISTRY This century's most famous equation, Einstein's special theory of relativity, transformed our comprehension of the nature of time and matter. Today, making use of the theory in a relativistic analysis of heavy molecules, that is, computing the properties and nature of electrons, is the work of chemists intent on exploring the mysteries of minute particles. The first work of its kind, Relativistic Effects in Chemistry details the computational and analytical methods used in studying the relativistic effects in chemical bonding as well as the spectroscopic properties of molecules containing very heavy atoms. The first of two independent volumes, Part A: Theory and Techniques describes the basic techniques of relativistic quantum chemistry. Its systematic five-part format begins with a detailed exposition of Einstein's special theory of relativity, the significance of relativity in chemistry, and the nature of relativistic effects, especially with molecules containing both main group atoms and transition metal atoms. Chapter 3 discusses the fundamentals of relativistic quantum mechanics starting from the Klein-Gordon equation through such advanced constructs as the Breit-Pauli and Dirac multielectron Hamiltonian. Modern computational techniques, of importance with problems involving very heavy molecules, are outlined in Chapter 4. These include the relativistic effective core potentials, ab initio CASSCF, CI, and RCI techniques. Chapter 5 describes relativistic symmetry using the double group symmetry of molecules and the classification of relativistic electronic states and is of special importance to chemists or spectroscopists interested in computing or analyzing electronic states of molecules containing very heavy atoms. An exceptional introduction to one of chemistry's foremost analytical techniques, Relativistic Effects in Chemistry is also evidence of the still unending reverberations of Einstein's revolutionary theory.

Author Biography

KRISHNAN BALASUBRAMANIAN is Professor of Chemistry at Arizona State University. He has received the Alfred P. Sloan Fellowship, Camille and Henry Dreyfus teacher-scholar and Fulbright Research awards. He is an author of about 400 journal publications.

Table of Contents

1 Relativistic Effects in Small Transition-Metal Clusters	1	(82)
1.1 Relativistic Effects in Transition-Metal Atoms	1	(2)
1.2 Relativistic Effects in Coinage-Metal Clusters	3	(43)
1.2.1 Experimental Studies on Cu(n), Ag(n), and Au(n)	4	(6)
1.2.2 Theoretical Studies on Cu(n), Ag(n), and Au(n)	10	(29)
1.2.3 Comparison of Coinage-Metal Clusters: Cu(n), Ag(n), and Au(n)	39	(7)
1.3 Electronic Structure of Palladium and Platinum Clusters	46	(15)
1.3.1 Pt(2)	46	(4)
1.3.2 Pd(2)	50	(4)
1.3.3 Pt(4) and Pd(4)	54	(7)
1.4 Electronic Structure of Rh(3) and Ir(3)	61	(22)
1.4.1 Rh(3)	61	(7)
1.4.2 Ir(3)	68	(15)
2 Relativistic Effects in Heteronuclear Diatomics of Main-Group p-Block Elements	83	(147)
2.1 Spectroscopic Properties and Potential-Energy Curves of Heavy Hydrides	84	(56)
2.1.1 GaH	84	(3)
2.1.2 GeH	87	(4)
2.1.3 AsH	91	(2)
2.1.4 SeH and SeH(+)	93	(4)
2.1.5 HBr and HBr(-)	97	(8)
2.1.6 InH	105	(1)
2.1.7 SnH	106	(4)
2.1.8 SbH	110	(4)
2.1.9 TeH	114	(1)
2.1.10 HI and HI(-)	115	(6)
2.1.11 TlH	121	(2)
2.1.12 PbH	123	(3)
2.1.13 BiH and BiH(+)	126	(14)
2.2 Spectroscopic Properties and Potential-Energy Curves of Heavy Halides	140	(41)
2.2.1 TlF	141	(4)
2.2.2 PbF	145	(1)
2.2.3 BiF	146	(9)
2.2.4 BiI	155	(1)
2.2.5 TlCl	155	(3)
2.2.6 PbCl	158	(3)
2.2.7 PbBr	161	(5)
2.2.8 PbI	166	(3)
2.2.9 SnCl	169	(2)
2.2.10 SnBr	171	(3)
2.2.11 SbF	174	(7)
2.3 Spectroscopic Properties and Potential-Energy Curves of Heavy Group IV Chalcogenides and Their Ions	181	(23)
2.3.1 SnO and SnO(+)	181	(3)
2.3.2 PbO and PbO(+)	184	(5)
2.3.3 SnS	189	(3)
2.3.4 PbS	192	(3)
2.3.5 SbO	195	(6)
2.3.6 BiO	201	(3)
2.4 Comparison of the Spectroscopic Properties of Heavy Hydrides	204	(8)
2.5 Comparison of the Spectroscopic Properties of Heavy Halides	212	(3)
2.6 Comparison of Heavy Chalcogenides	215	(15)
3 Relativistic Effects in Main-Group Clusters	230	(160)
3.1 Introduction	230	(1)
3.2 Methods of Investigation	231	(3)
3.2.1 Experimental Techniques	231	(2)
3.2.2 Theoretical Techniques of Calculation	233	(1)
3.3 Spectroscopic Properties and Potential-Energy Curves of Heavy Homonuclear Dimers (Ga(2) to Bi(2))	234	(96)
3.3.1 Ga(2)	234	(5)
3.3.2 Ge(2)	239	(7)
3.3.3 As(2)	246	(4)
3.3.4 Se(2)	250	(7)
3.3.5 Br(2) and Br(2)(+)	257	(11)
3.3.6 In(2)	268	(9)
3.3.7 Sn(2)	277	(3)
3.3.8 Sb(2)	280	(13)
3.3.9 Te(2)	293	(5)
3.3.10 I(2) and I(2)(+)	298	(16)
3.3.11 Tl(2) and Tl(2)(+)	314	(1)
3.3.12 Pb(2)	314	(7)
3.3.13 Bi(2)	321	(9)
3.4 Electronic Structure of Mixed Clusters	330	(4)
3.5 Spectroscopic Properties and Potential-Energy Surfaces of Trimers	334	(33)
3.5.1 Ga(3)	334	(4)
3.5.2 In(3)	338	(3)
3.5.3 Ge(3)	341	(4)
3.5.4 Sn(3)	345	(3)
3.5.5 Group V Trimers P(3)-Bi(3)	348	(7)
3.5.6 Se(3), Te(3), and Po(3)	355	(12)
3.6 Comparison of the Properties and Periodic Trends Among Dimers	367	(23)
4 Relativistic Effects on Molecules Containing Lanthanides and Actinides	390	(121)
4.1 Relativity and the Lanthanide Contraction	391	(6)
4.2 Ab Initio Theoretical Techniques for Lanthanide- and Actinide-Containing Molecules	397	(1)
4.3 Approximate Methods for Lanthanide and Actinide Molecules	398	(3)
4.3.1 Ligand Field Theory	398	(1)
4.3.2 Local Density Functional (LDF) Method	398	(2)
4.3.3 Neglect of Differential Overlap/ Spin-Orbit CI Method (INDO/S-CI)	400	(1)
4.4 Electronic Structure of Lanthanide Hydrides	401
4.4.1 YH and ScH	401	(6)
4.4.2 YH(2) and ScH(2)	407	(5)
4.4.3 Electronic States of LaH	412	(4)
4.4.4 LaH(+)	416	(5)
4.4.5 LaH(2)(+)	421	(5)
4.4.6 LaH(2)	426	(5)
4.4.7 HfH, ZrH, and TiH	431	(10)
4.4.8 HfH(2) and ZrH(2)	441	(7)
4.4.9 UH, UH(+), and UH(-)	448	(1)
4.4.10 AcH, TmH, LuH, and LrH	449	(2)
4.4.11 Ground-State Properties of Lanthanide Hydrides	451	(1)
4.5 Electronic States of Diatomic Lanthanide and Actinide Halides	452	(8)
4.5.1 LaF	453	(2)
4.5.2 YF and YCl	455	(1)
4.5.3 UF and UF(-)	456	(1)
4.5.4 Ground States of LaF-LuF	457	(3)
4.6 Lanthanide Oxides	460	(25)
4.6.1 LaO	460	(2)
4.6.2 CeO	462	(4)
4.6.3 PrO	466	(3)
4.6.4 SmO	469	(2)
4.6.5 EuO	471	(5)
4.6.6 GdO	476	(3)
4.6.7 DyO	479	(1)
4.6.8 HoO	480	(2)
4.6.9 TmO	482	(1)
4.6.10 YbO	482	(3)
4.7 Electronic Structure of Selected Lanthanide and Actinide Polyatomics	485	(18)
4.7.1 Polyatomic Oxides and Complexes	486	(3)
4.7.2 Uranocene and Actinocenes	489	(7)
4.7.3 Lanthanides and Actinides inside Carbon Cages (M@C(n), M@C(n)(+))	496	(7)
4.8 Conclusion	503	(8)
Index	511