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to Hydrogen

& Hydrogen Like Systems

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

1

Dr. D. Ilangeswaran, M. Sc., M. Phil., Ph. D.,

**Assistant Professor of Chemistry
**

Rajah Serfoji Govt. College

(Autonomous)

Thanjavur - 613005

**Hydrogen Like Atom
**

A system with a central nucleus and an

electron is known as H like atom.

In such systems the nucleus & the electron

are held together by means of electrostatic

attraction.

The wave function for either the H or H

like atoms (i.e. one e- systems) like He+, Li2+

can be calculated accurately.

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

3

Phil. 4 . the +vely charged proton is at the centre whereas the –vely charged e.is given in equation (1). -Z e2 (1) V= 4 r Dr.is at a distance. Ilangeswaran. and Z = 1 for H atom.The SWE for H atom 1. Ph..Sc. Where 40 is the permitivity.1126 × 10-10 C2 m-1 J-1. in atomic unit = 1. D. Potential energy In H atom.D. SI unit of it is 1. The potential energy of attraction between the nucleus & the e. “r” from the nucleus.. M.. M.

= me 5 . Ph.Phil.1 × 10-28 g) is negligible when compared to the mass of proton (1.. M.. Reduced Mass Generally the mass of an e. me = mp Dr. mp .Sc. me mp + me mp ..76 × 10-24 g). Ilangeswaran.(9. D.2. M.D. Due to this reason we may assume that the mass of an electron is roughly equal to the reduced mass of H atom.

M. .Phil..The SWE for H & H like atom is Using the values of m & V in this equation we get Transforming the above equation from Cartesian coordinate to polar coordinates (r. M. we get Dr.D. 6 . Ilangeswaran. D.. Ph.Sc.. ).

Equation (4) involves three variables. and occur in different terms of the above equation. ..Sc. Since the r term involves the potential energy.D. D. Where is the zenith angle and is azimuthal angle.. Separation of variables The dependence of r. and . Dr.Phil. M. r. it is possible to separate the partial differential equations. Ilangeswaran. one in each of the variables. M. 7 . Ph. ..

The position of a particle on the surface of a sphere of radius r is more conveniently determined in terms of two angular variables (coordinates) . It varies from 0 to 2π. P with the centre of the sphere. Ph.. The angle is the angle measured between the line r and the z axis.Phil. called the zenith angle. M.. Ilangeswaran. 8 . D... The angle is the angle measured in the xy plane between the x axis and the projection of the line r joining the particle. It varies from 0 to π.D. Dr.Sc. called the azimuthal angle and . M.

. Y(). r.. . and respectively. Z() Where R. The function R(r) is referred to as the radial function since it describes how the wave function varies with the radial distance. Dr. M. Ilangeswaran. ) = R(r). The following necessary derivatives can be obtained by proper differentiation.Phil. M. Y and Z are functions of only three variables r.The above mentioned variables can be separated by inserting into equation (3) a solution of the form (r. Ph. D.) represents angular part of the wave function.D. 9 . The functions Y() and Z() combined together as say Y(.Sc..

.Dr. Ph. M.Sc.Phil. D. Ilangeswaran.D. 10 .. M..

. this equation can be correct. Dividing equation (9) by sin2 Dr. Ilangeswaran.D. say m2. M. M. D. only if each side of this equation is equal to the same constant..Since the two sides of equation (7) are functions of different variables.Sc. Ph.. 11 .Phil.

Ilangeswaran..Phil. Ph.Sc..D. D.Dr. M. M. 12 ..

. M. Ilangeswaran.Dr. Ph. D. 13 ... M.Phil.Sc.D.

(13) and (14) each of which involves only one variable. Dr. These equations are called as ..D. D. M. 14 . Ph. r and equations respectively. M..Thus equation (4) is now separated into three ordinary differential equations (8)..Sc.Phil. Ilangeswaran.

. Ilangeswaran.Dr.Sc... M. M.D.Phil. D. 15 . Ph.

.Sc. M. M.Phil. Ph. D.Dr.. 16 .. Ilangeswaran.D.

D. 17 .Dr. D. M.Phil.Sc.. Ph... Ilangeswaran. M.

M.Phil.Atomic Orbitals • For an atom. M.D. Ph. a region where the probability of finding an electron is high • The orbital properties of greatest interest are size. the wave function defines an orbital. use Schrödinger’s equation • Find permissible energy levels for electrons around nucleus. D.. • For each energy level. and approximations are typically used Dr.. shape (described by wave function) and energy. 18 .Sc.. • Solution for multi-electron atoms is a very difficult problem. Ilangeswaran.

M. D.Phil. the wave function is a function of one quantum number.D. M. the 3-D hydrogen atom is a function of three quantum numbers Dr.The hydrogen atom The electron of the hydrogen atom moves in three dimensions and has potential energy (attraction to positively charged nucleus) The Schrodinger equation can be solved to find the wave functions associated with the hydrogen atom In 1-D particle in a box. 19 .. Ilangeswaran.Sc... Ph.

Sc. Rnl describes how wave function varies with distance of electron from nucleus Ylm describes the angular dependence of the wave function Subscripts n. Ilangeswaran..Wave functions of hydrogen The solution of the Schrodinger equation for the hydrogen atom is: n. . l and m are quantum numbers of hydrogen Dr.l r lm .m r .Phil.l .. Ph. M.D. Rn. . 20 .. M. D.

. the orbital becomes larger and the electron is farther from the nucleus As n increases. Ilangeswaran.Sc..D. the orbital has higher energy (less negative) and is less tightly bound to the nucleus Dr. M. D. n Has integral values of 1. 21 . Ph.3…… and is related to size and energy of the orbital As n increases.2.Phil.. M.Principal quantum number.

M. Ph.. Ilangeswaran... l Can have values of 0 to n-1 for each value of n and relates to the angular momentum of the electron in an orbital The dependence of the wave function on l. p orbital d orbital 22 .D.Phil. D.Sc. determines the shape of the orbitals The value of l. M.Angular quantum number. for a particular orbital is commonly assigned a s orbital letter: 0–s 1–p 2–d 3–f Dr.

2 .1 Dr.Phil..D. D. m=-2. including zero and relates to the orientation in space of the angular momentum. M. Ilangeswaran...0. ml Can have integral values between l and . d orbital: 23 l=2. s orbital: l=0. M.-1.Sc.l. Ph. m=0 p orbital: l=1.0. m=-1.1.Magnetic quantum number.

.…(n-1) number n ml magnetic -l ..l+1.…0.Phil.Sc. Allowed States 24 .2..2. M.. quantum number Any number l Angular quantum 0. M.Calculation of quantum numbers Quantum Numbers Name Allowed Values n principal 1.D. 2 l +1 quantum number l Dr. D. Ph..1.( l-1). Ilangeswaran.3….

Shells and subshells All states with the same principal quantum number are said to form a shell. M. 0–s 1–p 2–d 3-f 25 . Ilangeswaran. D.. Ph. M..Phil.Sc.. the states having specific values of both n and l are said to form a subshell Shell (n) l Subshell symbol 1 0 1s 2 2 3 3 3 0 1 0 1 2 2s 2p 3s 3p 3d Dr.D.

0 1s 2 3 Dr. 26 . M. Ph. Ilangeswaran.Sc. D..D.Phil.. M..Example n l ml Wave Function Subshell symbol 1 0 0 Y1.0.

Ilangeswaran.. M. 3 ao 1 0.. D.. 27 .109 x10 31 kg k Coulomb' s constant 8. .0 .0 r . 529 x 10 m mke2 h 1. M.602 x10 19 Cb Dr.988 x109 Jm / Cb 2 e electron charge 1.Sc.Phil.0. 4 1/ 2 1/ 2 r exp ao 2 10 ao 0 .D.055 x10 34 Js 2 m mass of electron 9. Ph.Orbital shapes Solution of the Schrodinger wave equation for a one electron atom : 1 1.

M. M. D... Ilangeswaran.D. r r90% 28 . Ph.Phil.Electron probability distribution Wave function Probability Y1s2 Y1s r A spherical surface that contains 90% of the total electron probability (orbital representation) Dr.Sc..

D. Ilangeswaran.Sc.1 2p Dr.-1 2p 2 1 0 Y2..0..1.0 1s 2 0 0 Y2. M.Other orbitals n l ml Wave Function Subshell symbol 1 0 0 Y1.. M. Ph.1.D.1.0 2s 2 1 -1 Y2.0. 29 .Phil.0 2p 2 1 1 Y2.

Allowed energies of hydrogen The energy En of the wave function Ynlm depends only on n: 4 me En 2 2 2 8 o h n m . D.Sc.. M.D.electron charge h – Planck constant – permittivity of free space Because n is restricted to integer values. M. energy levels are Dr. 30 quantized .. Ilangeswaran. Ph.mass of electron e ..Phil.

This means that the electron has two spin states. M.. ms This quantum number only has two values: ½ and –½.. D..Atomic Orbitals: Multi-electron atoms Electron spin quantum number. Ph.D. 31 . M. thus producing two oppositely directed magnetic moments This quantum number doubles the number of allowed states for each electron.Sc. Pair of electrons in a given orbital must have opposite spins Dr. Ilangeswaran.Phil.

1.0 2p 2 1 1 Y2.0.1.. D. (-1/2) 32 .0 2s 2 1 -1 Y2. M.D. ms (1/2).1.0...Phil.1 2p Dr. Ilangeswaran.-1 2p 2 1 0 Y2. M.0 1s 2 0 0 Y2.Example n l ml Wave Function Subshell symbol 1 0 0 Y1.Sc. Ph.

ml and ms Aufbau principle Electrons fill in the orbitals of successively increasing energy.Phil..Sc.. n=2)..Pauli exclusion principle No two electrons can have the same set of quantum numbers: n. Ph. D. l. M. Ilangeswaran. starting with the lowest energy orbital Hund’s rule For a given shell (example. 33 .D. the electron occupies each subshell one at a time before pairing up Dr. M.

M.. M.Orbital energies: multi-electron atoms Energy depends on both n and l Dr. 34 . D. Ilangeswaran.D..Sc. Ph..Phil.

1.. (-1/2) 35 .Sc.0. M.1. Ilangeswaran. D.1 2p Dr.-1 2p 2 1 0 Y2.0 2p 2 1 1 Y2.0.Example: Nitrogen (1s22s22p3) n l ml Wave Function Subshell symbol 1 0 0 Y1. M.0 2s 2 1 -1 Y2.0 1s 2 0 0 Y2.Phil.. Ph. ms (1/2)..1.D.

-1 2p 2 1 0 Y2.0.0 2s 2 1 -1 Y2. D.Phil.Sc. Ilangeswaran.1 2p Dr. M...Example: Carbon n l ml Wave Function Subshell symbol 1 0 0 Y1. M. (-1/2) 36 .1.0 1s 2 0 0 Y2. ms (1/2).0 2p 2 1 1 Y2.1. Ph.0.1.D..

Ilangeswaran.Phil.. M.Atomic Orbitals: Summary In the quantum mechanical model. D..Sc. 37 . Ph.. M. the electron is described as a wave. This leads to a series of wave functions (orbitals) that describe the possible energies and spatial distribution available to the electron The orbitals can be thought of in terms of probability distributions (square of the wave function) Dr.D.

Phil. Ilangeswaran..Sizes. and orientations of orbitals n determines size.. D.Sc. M..D. Shapes. 38 . Ph. M. l determines shape ml determines orientation Dr.

D.Sc.Phil. 2s one node. Ph. Ilangeswaran.Nodes in orbitals: s orbitals: 1s no nodes. 39 . M.... M. 3s two nodes Dr.D.

M.that is shown for a p orbital refers to the mathematical sign of the wavefunction.D. not electric charge! Dr.Phil. 40 .. D.Sc. Ilangeswaran.. M. Ph.Nodes in orbitals: 2p orbitals: angular node that passes through the nucleus Orbital is “dumb bell” shaped Important: the + and ..

41 .Nodes in orbitals: 3d orbitals: two angular nodes that passes through the nucleus Orbital is “four leaf clover” shaped d orbitals are important for metals Dr.... M. M. D. Ilangeswaran.Phil.D. Ph.Sc.

D.Sc. (spin up) (spin down) Dr. Ph. M. 42 .. Ilangeswaran.. M.Phil..D. like its charge and mass.The fourth quantum number: Electron Spin ms = +1/2 (spin up) or -1/2 (spin down) Spin is a fundamental property of electrons.

M.Electrons in an orbital must have different values of ms This statement demands that if there are two electrons in an orbital one must have ms = +1/2 (spin up) and the other must have ms = -1/2 (spin down) This is the Pauli Exclusion Principle An empty orbital is fully described by the three quantum numbers: n. M. l. D. Ilangeswaran. ml and ms Dr...D. 43 .Sc.Phil. Ph. l and ml An electron in an orbital is fully described by the four quantum numbers: n..

Phil.D. M. 44 . we can treat the motion of the nuclei classically or quantum mechanically Dr.Born-Oppenheimer Approximation • the nuclei are much heavier than the electrons and move more slowly than the electrons • in the Born-Oppenheimer approximation. M. D.. Ilangeswaran. the energy as a function of the geometry) • on this potential energy surface. Ph. Rnuc.Rnuc) and energy E(Rnuc) • E(Rnuc) is the potential energy surface of the molecule (i. we freeze the nuclear positions.e..Sc. Yel(rel.. and calculate the electronic wavefunction.

.D. M.. E H el el el * ˆ Y el Hel Yel d * Y el Yel d • E depends on the nuclear positions through the nuclearelectron attraction and nuclear-nuclear repulsion terms • E = 0 corresponds to all particles at infinite separation Dr. Ph. Ilangeswaran.Phil. 45 .Born-Oppenheimer Approximation • freeze the nuclear positions (nuclear kinetic energy is zero in the electronic Hamiltonian) ˆ H el electrons i 2 2 electrons i 2me i nuclei A e2 Z A electrons e2 nuclei e2 Z A Z B riA rij A B rAB i j • calculate the electronic wavefunction and energy ˆ Y EY . M..Sc. D.

Nuclear motion on the Born-Oppenheimer surface • Classical treatment of the nuclei (e.. molecular vibrations) ˆ Ytotal Yel nuc . a 2 R nuc / t 2 • Quantum treatment of the nuclei (e. 46 .D.Sc. Ilangeswaran. D..Phil. M. Ph.g.g. M.. F E / R nuc . classical trajectories) F ma. H nuc nuc nuc ˆ H nuc nuclei A 2 E (R nuc ) 2m A 2 Dr.

D. Ph. r3 .) (r1 ) (r2 ) (r3 ) • if we use the variational energy.. solving the many electron Schrödinger equation is reduced to solving a series of one electron Schrödinger equations • each electron interacts with the average distribution of the other electrons Dr.. 47 ..Phil. r2 .D. M. M.Sc.Hartree Approximation • assume that a many electron wavefunction can be written as a product of one electron functions Y (r1 . Ilangeswaran.

. Ph. M...Sc. Ilangeswaran. D.1)|2.Hartree-Fock Approximation • the Pauli principle requires that a wavefunction for electrons must change sign when any two electrons are permuted – since |Y(1. Y(1.2)|2=|Y(2. 48 .2)=Y(2.Phil. M.D.1) (minus sign for fermions) • the Hartree-product wavefunction must be antisymmetrized • can be done by writing the wavefunction as a determinant – determinants change sign when any two columns are switched Y 1 (1) 1 (2) 1 (n) 1 2 (1) 2 (2) 2 (n) n n (1) n (1) n (n) 1 2 n Dr.

.Sc.. 49 . D.D. spin up) or beta spin (. Ilangeswaran. Ph. spin down) • each spatial orbital can be combined with an alpha or beta spin component to form a spin orbital • thus.. M. at most two electrons can be in each spatial orbital Dr. each electron must be in a different spin orbital (or else the determinant is zero) • an electron has both space and spin coordinates • an electron can be alpha spin (. M. .Phil..Spin Orbitals • each spin orbital I describes the distribution of one electron • in a Hartree-Fock wavefunction.

50 . Ilangeswaran.Phil. D. M. * i j d ij • yields the Fock equation Fˆ i ii Dr. M...Fock Equation • take the Hartree-Fock wavefunction Y 1 2 n • put it into the variational energy expression Evar * ˆ Y HYd * Y Yd • minimize the energy with respect to changes in the orbitals while keeping the orbitals orthonormal Evar / i 0.D. Ph..Sc.

Sc.. M. D.Phil. 51 ..Fock Equation Fˆ i ii • the Fock operator is an effective one electron Hamiltonian for an orbital • is the orbital energy • each orbital sees the average distribution of all the other electrons • finding a many electron wavefunction is reduced to finding a series of one electron orbitals Dr.D.. M. Ph. Ilangeswaran.

Sc..Phil.D. Ph. Ilangeswaran. M..Fock Operator ˆ V ˆ Jˆ K ˆ Fˆ T NE • kinetic energy operator 2 2 ˆT 2me • nuclear-electron attraction operator ˆ V ne nuclei A e2 Z A riA Dr. D. M.. 52 .

D. 53 .Fock Operator ˆ V ˆ Jˆ K ˆ Fˆ T NE • Coulomb operator (electron-electron repulsion) electrons Jˆ i { j e2 j rij j d }i • exchange operator (purely quantum mechanical arises from the fact that the wavefunction must switch sign when you exchange to electrons) electrons ˆ { K i j e2 j rij i d } j Dr.Sc. M.. Ilangeswaran...Phil. M. D. Ph.

obtain an initial guess for all the orbitals i use the current I to construct a new Fock operator solve the Fock equations for a new set of I if the new I are different from the old I.Sc..Solving the Fock Equations Fˆ i ii 1. M. 3. 54 . Dr. Ph. 4. M.Phil.. D.. Ilangeswaran. go back to step 2. 2.D.

Phil.D. d orbitals radial part somewhat different..Sc. M.g. Ph. M. p. 55 . electrostatic repulsion and exchange interaction with other electrons) Dr... D. Ilangeswaran.Hartree-Fock Orbitals • • • • for atoms. because of interaction with the other electrons (e. the Hartree-Fock orbitals can be computed numerically the ‘s resemble the shapes of the hydrogen orbitals s.

bonding and anti-bonding orbitals Dr. D. M.. M.Sc.D. 56 . Ilangeswaran.Hartree-Fock Orbitals • • • for homonuclear diatomic molecules. the Hartree-Fock orbitals can also be computed numerically (but with much more difficulty) the ‘s resemble the shapes of the H2+ orbitals . ... Ph.Phil.

D. 57 . D.g. M. Ilangeswaran.LCAO Approximation • • • • numerical solutions for the Hartree-Fock orbitals only practical for atoms and diatomics diatomic orbitals resemble linear combinations of atomic orbitals e.Sc. Ph...Phil. M.. sigma bond in H2 1sA + 1sB for polyatomics. approximate the molecular orbital by a linear combination of atomic orbitals (LCAO) c Dr.

Basis Functions

c

•

•

•

•

**’s are called basis functions
**

usually centered on atoms

can be more general and more flexible than atomic

orbitals

larger number of well chosen basis functions yields

more accurate approximations to the molecular

orbitals

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

58

**Roothaan-Hall Equations
**

•

choose a suitable set of basis functions

c

•

plug into the variational expression for the energy

Evar

•

* ˆ

Y

HYd

*

Y

Yd

**find the coefficients for each orbital that minimizes
**

the variational energy

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

59

**Roothaan-Hall Equations
**

•

•

•

•

•

**basis set expansion leads to a matrix form of the
**

Fock equations

F Ci = i S Ci

F – Fock matrix

Ci – column vector of the molecular orbital

coefficients

I – orbital energy

S – overlap matrix

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

60

M.Phil.. 61 .D.. Ph. D.. Ilangeswaran.Sc.Fock matrix and Overlap matrix • Fock matrix F Fˆ d • overlap matrix S d Dr. M.

Ph.Sc. 62 .Phil.D. Ilangeswaran.. M..Intergrals for the Fock matrix • Fock matrix involves one electron integrals of kinetic and nuclear-electron attraction operators and two electron integrals of 1/r ˆ V ˆ ) d h (T ne • • one electron integrals are fairly easy and few in number (only N2) 1 ( | ) (1) (1) (2) (2)d 1d 2 r12 two electron integrals are much harder and much more numerous (N4) Dr.. D. M.

solve F Ci = i S Ci for a new set of Ci 6. M. use the current Ci to construct a new Fock matrix 5. calculate all the one and two electron integrals 3. go back to step 4. D. if the new Ci are different from the old Ci.Sc..Phil. 63 .Solving the Roothaan-Hall Equations 1.. Dr. obtain an initial guess for all the molecular orbital coefficients Ci 4. Ilangeswaran. M. Ph.. choose a basis set 2.D.

. 64 .Sc. since each orbital depends on all the other orbitals. Ilangeswaran. and they are adjusted until they are all converged calculating all two electron integrals is a major bottleneck. D..Solving the Roothaan-Hall Equations • • • • also known as the self consistent field (SCF) equations. Ph. because they are difficult (6 dimensional integrals) and very numerous (formally N4) iterative solution may be difficult to converge formation of the Fock matrix in each cycle is costly. M.. M. since it involves all N4 two electron integrals Dr.Phil.D.

M.Summary • • • • • start with the Schrödinger equation use the variational energy Born-Oppenheimer approximation Hartree-Fock approximation LCAO approximation Dr. 65 ..Sc.D. Ph.Phil.. D. Ilangeswaran.. M.

Phil.. Ph.D.Sc. M. Ilangeswaran.. D.The Pauli principle and Slater determinants Dr. M.. 66 .

. D. Ph. M.Phil.. Ilangeswaran.Sc.Dr.D. M.. 67 .

Sc. Ph..Dr. Ilangeswaran. 68 . M. M.D.Phil.. D..

. M. D. Ilangeswaran.. 69 .Sc.Dr.Phil.D.. M. Ph.

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