10978-高等固体物理[完整版]-中科大研究生课程[hejizhancom].ppt

Valence Bond Theory Bond = overlap of atomic orbitals (AOs) Extent of overlap = strength of bond If orbital overlapping has direction, bond will have direction Valence AOs in a molecule are different than those in unbonded atoms. HYBRIDIZATION, a mixing of AOs, produces hybrid orbitals of equal energy but hybrid character #AOs mixed = # hybrid orbitals formed Hybrid orbitals s + p + p + p = sp3 + sp3 + sp3+ sp3 head on overlap produce sigma bonds sideways overlap of unhybridized p orbitals produce pi bonds How will this affect the character of s and p bonds? Molecular Orbital Theory (MOT) Electrons in a molecule are in a collective Bonding orbitals are formed from the addition of AOs (lower energy than AOs) Antibonding orbitals are formed from the subtraction of AOs (higher energy than AOs) Filling of MO diagram obeys rules of AO diagram Bond order = ? (#bonding e-s - #antibonding e-s) Bond order = 0 indicates the species will not exist. Comparison of Two Models VBT describes organic chemistry very well MOT describes small molecules with resonance and the paramagnetic character of oxygen; allows the prediction of whether a species will exist (stability) MOT已是量化的主流， Gaussian软件落户千万实验室 JOHN A. POPLE (1925---2005) 1998 Nobel Laureate in Chemistry for his development of computational methods in quantum chemistry Iron-based superconductors ReFeMO series (Re=La, Sm, Gd, Pr, Ce…; M=As, P…) LiFeAs ReFe2As2 series (Re=Eu, Sr, Ba, Ca…) FeSe series Time versus Tc 多铁- Multiferroics Two contrasting order parameters Magnetization: time-reversal symmetry broken Polarization: inversion symmetry broken Recently discovery in the coexistence and gigantic coupling of antiferromagnetism and ferroelectricity in frustrated spin systems such RMnO3 and RMn2O5 (R=Tb, Ho , …) revived interest in “multiferroicity” TC TN Frustrated magnetic systems. TbMnO3: Kimura et al., Nature 426, 55, (2003) TbMn2O5: Hur et al., Nature 429, 392 (2004) Magnetism and ferroelectricity coexist