Text book: Applied Mathematics for Physical Chemistry, Barrante, 3rd , 2004.

Reference books: ♦ Chemistry Maths Book, Steiner, 2004 ♦ Physical Chemistry, A Molecular Approach, McQuarrie and Simon, 1997 • • • Homework (30%) Midterm (30%) Final (40%)

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----Lecture note in PDF file is emailed to everyone before class--Put more time on listening Follow math logical procedures and techniques carefully

任課老師 : 朱超原 <cyzhu@mail.nctu.edu.tw> 助教: 林雨德 <adudu.fish@gmail.com>

Example in Math Example.1 (in teaching) ⎡1 ⎢1 ⎢ ⎢M ⎢ ⎣1 1 L 1⎤ 1 L 1⎥ ⎥ M M M⎥ ⎥ 1 1 1⎦ 1 + 2 + 3 + ••• + n = (n+1)n/2 [n 2 −n +n 2 ] Problem 1: 1 + 5 + 9 + 13 + ··· + [1+4(n-1)] = ? Problem 2: Problem3 : ……… Infinite applications Gap may appear from learning to applications 1 + 2 + 4 + 7 + ··· + [1+n(n-1)/2]= ? .

Problem 2: 1 + 2 + 4 + 7 + ··· + [1+n(n-1)/2]= n+S(n-1)? How to construct matrix to solve the following k (k + 1) Sn = ∑ =? 2 k =1 n Design matrix n ⎤ L L n − 1⎥ ⎥ L n − 2⎥ ⎥ M M ⎥ 1 ⎥ L ⎦ 2 3 ⎡1 ⎢n 1 2 ⎢ ⎢n n − 1 1 ⎢ M M ⎢M Sum each row = 1+2+3 +···n=n(n+1)/2 ⎢n n − 1 n − 2 ⎣ Sum all rows: Total =n*n(n+1)/2 .

Design matrix 2 3 ⎡1 ⎢n 1 2 ⎢ ⎢n n − 1 1 ⎢ M M ⎢M ⎢n n − 1 n − 2 ⎣ n ⎤ L n − 1⎥ ⎥ L n − 2⎥ ⎥ M M ⎥ 1 ⎥ L ⎦ L Sum over upper off-diagonal plus diagonal matrix elements Sum over lower off-diagonal S n = ∑ n k =1 k ( k + 1) 2 A n = n ( n − 1 ) + ( n − 1 )( n − 2 ) + L + 2 ⋅ 1 = ∑ n −1 k =1 ( k + 1) k = 2 S n − ( n + 1) n n ⋅ n ( n + 1) 1 = 3 S n − ( n + 1) n ⇒ S n = n (n + 1 )(n + 2 ) 2 6 .

Example.2 (in teaching) 1 − a n +1 1 + a + a2 + a3 + L + an = 1− a Problem (in application) a 2 + a 4 + L + a 2n = ? L a 2 + a 4 + a 7 + L + a [n ( n +1) / 2+1] = ? .

After warming up .

I. Review of differentiation and integration • Introduction • Review of differential calculus • Review of integral calculus • Graph .

T.I-1. V. Introduction Hot coffee in closed container Study from point of view Physical Chemistry I Physical Chemistry II Physical Chemistry III State of function f (P. n) = 0 ? .

n)=0 Interface between different phases f2(P. T. V. V. n PV=nRT Solid P. n Liquid P.V. n Very dilute gas P. V. V.V. V. T. T. n)=0 Can we find f (P. T. n) = 0 ? . T. T. T. V. T. n f1(P. n)=0 f3(P.Physical Chemistry I Ideal gas Dense gas P.

L ) = 0 . n . c .Macroscopic thermodynamic method Derive f (P. V . n) from experiment Van Der Waals equation ⎛ an 2 ⎜P + 2 ⎜ V ⎝ ⎞ ⎟ (V − nb ) = nRT ⎟ ⎠ Try various equations with two parameters f (P . a . T. b ) = 0 Improve accuracy with more parameters involved f (P . b . T . n . V. a . V . T .

we have to solve Schrödinger equation ˆ H Ψk = E k Ψk h2 h2 2 ˆ H = −∑ ∇ Rα − 2 me α =1 2 M α Nn time ⎡ Z e2 2 α ∑ ∇ i − ∑1 ∑ ⎢ r − R r r i =1 α = i =1 ⎢ i α ⎣ Ne Nn Ne Nn Nn ⎤ Ne Ne e2 Zα Z β e 2 ⎥+∑∑ r r +∑ ∑ r r ⎥ j =1 i < j ri − r j α =1 β <α Rα − Rβ ⎦ .Physical Chemistry II Temperature Energy In order to get energy levels Ek.

N . V. n) from theory Partition function Q (V . T )= ∑ j e −E j k BT From physical chemistry II ⎛ ∂ ln Q ⎞ P = k BT ⎜ ⎟ ⎝ ∂V ⎠T .N 2 . T.Physical Chemistry III Microscopic thermodynamic method Derive f (P.

b . a .The most general and the best state of equation f (P . c . V . L ) = 0 Combine experiment and theory Combine 物化一 and 物化三 through 物化二 . n . T .

mathematics . weak. forces must be considered in theory. mathematics At very high temperature. Gravitation. Chemistry (or physics) is now supposed to obey Fermi-Dirac or Bose Einstein statistics. atom star. quark star. nuclear star. and electromagnetic. super-conductor and superfluid can happen.Extreme situations : for both experiment and theory At room temperature and pressure. and blackbody show up. most chemistry is supposed to obey Boltzmann statistics. mathematics At very low temperature ( T 0 ).

Baby steps A single variable differential calculus A single variable integral calculus .

y---dependent variable y = f (x ) f----function form (in math) y = y (x ) (In physics and chemistry) Example: ρ = ρ(T) Definition of the first derivative dy df ( x ) f (x + ∆x ) − f (x ) y′ = = f ′( x ) = = lim dx dx ∆x ∆x → 0 .I-2. Review of differential calculus Naming: x –independent variable.

Example 1 (Simplest) f ′ (x ) = y = f ( x ) = ax + b linear lim [a ( x ∆x→ 0 + ∆ x ) + b ] − [ax + b ] = ∆x lim ∆x→ 0 a∆x = a ∆x Example 2 f ′(x) = lim ∆x→0 y = f ( x ) = ax 2 2 + bx + c quadratic 2 [a(x + ∆x) (2ax + b)∆x + a(∆x) = 2ax + b + b(x + ∆x) + c − ax2 + bx + c = lim ∆x ∆x ∆x→0 ][ ] Example 3 y = f ( x ) = sin x sin function f ′( x ) = lim ∆x → 0 sin ( x + ∆x ) − sin ( x ) 2 cos ( x + ∆x / 2 )sin (∆x / 2 ) = lim = cos x ∆x ∆x ∆x → 0 .

Example 4 y = f ( x ) = arcsin x arcsin function y = f (x) = arcsinx ⇔ sin y = x dx on both side d (sin y ) dx = =1 dx dx d (sin y ) dy ⎡ d (sin y ) ⎤ = ⎢ dy ⎥ = f ′( x ) cos y = 1 dx dx ⎣ ⎦ Calculate dy Final f ′( x ) = 1 = cos y 1 1 − sin 2 y = 1 1− x2 .

Certain rules z = g (x ) y = f (x ) d ( yz dx )= y dz dy + z dx dx or d ( fg dx )= f dg df g + dx dx Chain rule y = f (u ( x )) dy df (u ( x )) df (u ( x )) du df (u ) du = = = dx dx du dx du dx Example 5: proof d (y / z ) dx .

Higher-order derivatives y = f (x ) z = g (x ) d ( yz ) = y ′z + y z ′ dx d 2 ( yz ) d ( y ′z + y z ′ ) = = y ′′z + 2 y ′z ′ + y z ′′ 2 dx dx Example 6: proof d n dx ( yz ) = n ∑ n k =0 ⎛ n ⎞⎡ d k y ⎤ ⎡ d n−k z ⎤ ⎜ ⎟⎢ ⎜ k ⎟ dx k ⎥ ⎢ dx n − k ⎥ ⎝ ⎠⎣ ⎦⎣ ⎦ Try various functions for differential calculus as Mental training game .

(a) – (t) .Homework 1-1 Page53-54 Problem 1.

Review of integral calculus Indefinite integral F (x ) = ∫ f ( x )dx dF ( x ) = f (x ) dx x2 xdx = + C 2 x3 2 x dx = + C 3 x n +1 x dx = + C n + 1 n integrand Example 1 f (x) = x f (x) = x2 L f (x) = x n F F L F (x ) = ∫ (x ) = ∫ (x ) = ∫ Example 2 f ( x ) = sin x f (x) = e−x ∫ sin xdx = − cos x + C F ( x ) = ∫ e − x dx = − e − x + C F (x ) = .I-3.

Most important rule: integration by part ∫ u (x ) or write as dv ( x ) du ( x ) dx = u ( x )v ( x ) − ∫ v ( x ) dx dx dx ∫ uv′dx = uv − ∫ vu′dx ∫ udv = uv − ∫ vdu dv( x ) dv( x ) Proof F ( x ) ≡ ∫ u ( x ) dx ⇒ F ′( x ) = u ( x ) dx dx du ( x ) H ( x ) ≡ u ( x )v( x ) − ∫ v( x ) dx ⇒ H ′( x ) = u′v + uv′ − vu′ = uv′ dx Final F ′( x ) = H ′( x) ⇒ F ( x ) = H ( x ) + C .

Example 3 xe− x dx = ∫ xd − e− x = x − e− x − ∫ − e− x dx = −( x + 1)e− x ∫ Example 4 2 2 2 ⎛ x2 ⎞ x2 x x x ∫ xlnxdx= ∫ lnxd⎜ 2 ⎟ = 2 lnx − ∫ 2 d(lnx) = 2 lnx − 4 ⎜ ⎟ ⎝ ⎠ ( ) ( ) ( ) Example 5 1 1 ⎡ 1 1 ⎤ 1 dx = −∫ − = ∫ (a − x)(b − x) ⎢ a − x b − x ⎥ (a − b) [ln(a − x) − ln(b − x)] (a − b) ⎣ ⎦ .

Change of variable (substitution) Example 6 1 ⎯ ∫ e dx ⎯ ⎯ ⎯ ⎯ ⎯ → a ax ax = y ⇒ adx = dy 1 y 1 ax ∫ e dy = a e = a e y Example 7 d sinx y2 sin2 x ⎯ ∫ sinx cosxdx= ∫ sinx dx dx ⎯⎯⎯⎯⎯⎯ →∫ ydy= 2 = 2 sinx= y ⇒ d sinx dy = dx dx Calculation in heart sin2 x ∫ sinx cosxdx= ∫ sinxdsinx = 2 .

Example 8 (luck case) ax 1 1 ax ax ax ∫ e sinbxdx = a ∫ sin bxde = a e sinbx − b∫ e cosbxdx 1 ⎡ ax b ⎤ = ⎢e sin bx − ∫ cosbxdeax ⎥ a a⎣ ⎦ 1 ⎡ ax b ax ⎤ ax = ⎢e sin bx − e cos x − ∫ e d cosbx ⎥ a⎣ a ⎦ [ ] ( ) 1 ⎡ ax b ax ⎤ ax == ⎢e sin bx − e cos x + b∫ e sin bxdx ⎥ a⎣ a ⎦ Algebraic calculation ( ) eax eax sin bxdx = 2 2 [a sin bx − b cosbx] ∫ a +b .

A lot of methods for integration. but most important is checking If you get Check ∫ f (x)dx = F (x) F ′( x) = f (x) ∫e − x2 dx has no compact form with simple function Integration is more difficult than differentiation .

Example 9 ∞ x 2 n+1e−ax ∫ 0 2 1 n −αy y=x dx ⎯⎯ → ∫ y e dy ⎯ 20 2 ∞ Method 1 n n n−1 −αy n −αy I n (a ) = ∫ y e dy = ∫ y e dy = I n−1 (a ) a a0 0 ∞ ∞ n! n! I n (a ) = n I 0 (a ) = n+1 a a Method 2 I 0 (a ) = ∫ e 0 ∞ ∞ −α y a>0 1 dy = a ∞ dI 0 (a ) 1 −α y = ∫ (− y )e dy = − 2 ⇒ da a 0 ∞ ∫ ( y )e 0 −α y 1 dy = 2 a Continue derivative ∫ (y) e n 0 −α y 1 ⋅ 2 ⋅ 3L n dy = a n +1 .

Example 10 Method 1 I n (a ) = ∫ x e 0 ∞ 2 n − ax 2 dx (2n −1) x 2n−2e−ax2 dx = (2n −1)I (a ) 1 2 n −1 − ax 2 I n (a ) = n −1 ∫ x de = (2a) ∫ (− 2a ) 0 2a 0 ∞ ∞ (2 n − 1)!! I (a ) I n (a ) = (2 a )n 0 I 0 (a ) = ∫ e 0 ∞ − ax 2 dx = ? .

Definite integral ∞ ∫e 0 −ax2 1 π dx = 2 a Derive ∞ 0 ∫e − ax 2 dx = ⎡∞ ⎢∫ e ⎢0 ⎣ − ax 2 ⎤ dx ⎥ ⎥ ⎦ 2 ⎡∞ ⎢ ∫ e − ax ⎢0 ⎣ 2 ∞ ∞ π /2 ∞ ⎤ 2 2 π − ax − ay − ar 2 dx ⎥ = ∫ e dx ∫ e dy = ∫ d ϕ ∫ re dr = 4a ⎥ 0 0 0 0 ⎦ 2 .

Homework 1-2 Page71-72 Problem 1. (a)– (j) Problem 2. (a) – (t) .

I-4. Graph Graphic meaning of derivative ---.line tangent to a curve f (x) x* x2 x1 x0 x f ′(x1 ) = tanθ1 f ′(x0 ) = tanθ0 .

Application to maximum-minimum of function f ′(x) = tanθ = 0 ⇒ θ = 0 Extreme f(x) x0 x2 x1 x0 f ′′ ( x 2 ) > 0 f ′′ ( x1 ) < 0 f ′′ ( x 0 ) = 0 x1 x2 x Minimum Maximum Inflection point 1 2 f (x ) = f (x i ) + f ′′ ( x i )( x − x i ) 2! .

x > 0 d 2 f ( x) = 12x⎨ 2 dx ⎩< 0. x < 0 .Example 1 (x) = 2x3 − 6x + 2 y= f df (x) = 6x2 − 6 = 0 ⇒ x = 1 x = −1 dx minimum maximum ⎧> 0.

Definite integral First do indefinite integral F (x ) = ∫ f (x )dx ∫ f (x )dx a b = F (b ) − F (a ) Graphic meaning of definite integral ---.area of shaded region ff((u )) x a b u a Area can be minus or plus 2π b 2π x ∫ sin xdx = [− cos x]0 = 0 0 .

(a)– (j) .Homework 1-3 Page 55 Problem 4.