CSO 202A Atoms Molecules and Photons

Home , Arieh Warshel, Eric Betzig, Gerhard Ertl, Martin Karplus, Michael Levitt, Walter Kohn

CSO 202A

Atoms Molecules and Photons

Piazza sign-up link: piazza.com/iitk.ac.in/secondsemester2017/cso202 Piazza class link: piazza.com/iitk.ac.in/secondsemester2017/cso202/home

Instructors: Dr. Manabendra Chandra and Dr. Madhav Ranganathan

Lec: M,W,Th: 12:00-12:50 L3 CSO 202A : Atoms Molecules and Photons

Tutors: Sourav Karmakar ([email protected]) Navin Subba ([email protected]) Aqeel Malani ([email protected])

Tut: Friday: 17:00-17:50 T207-209

Grading scheme:

Quiz-1 (45 mins): 15% (module 1) 3rd Feb. 2017 Quiz-2 (45 mins): 15% (module 3) 31 st Mar. 2017

MidSem (2 hrs): 35% (module 1 + module 2) EndSem (2 hrs) : 35% (module 3 + module 4) CSO 202A : Atoms Molecules and Photons Path-breaking research works in the field of chemical reaction dynamics

2007: Gerhard Ertl "for his studies of chemical processes on solid surfaces" 2013: Martin Karplus, Michael Levitt and Arieh Warshel "for the development of multiscale models for complex chemical systems". 2014: Eric Betzig, Stefan W. Hell and William E. Moerner "for the development of super-resolved fluorescence microscopy".

: Chemistry with Supercomputers with Chemistry : 4 Module

: Catalytic Reactions on Solid Surfaces Solid on Reactions Catalytic : 3 Module

Pulsed Lasers Pulsed

: Ultrafast Chemical Reaction Dynamics with Ultrashort- Ultrashort- with Dynamics Reaction Chemical Ultrafast : 2 Module

Module 1 Module : Chemical Reaction Dynamics with Molecular Beams Molecular with Dynamics Reaction Chemical :

Module 4 3 Module CSO 202A CSO

Module 1 Module Module 2

Course plan Course CSO 202A : Atoms Molecules and Photons and Molecules Atoms : 202A CSO CSO 202A : Atoms Molecules and Photons

Module 1 :

Chemical Reaction Dynamics with Molecular Beams CSO 202A : Atoms Molecules and Photons

Consider the reaction:

This way of writing down chemical reactions, using arrows and symbols, is ‘incomplete’

 Do rates depend on internal quantum states of the reactants?  What are the internal quantum states of the products?  What is the dependence of chemical reactivity on molecular orientation? Dependence on the impact of collision?  What are the nature of reaction intermediates and their subsequent decay dynamics in case of complex polyatomic molecular reactants? CSO 202A : Atoms Molecules and Photons

Answers can be found by doing experiments using crossed molecular beam technique

2Na + O2 → Na2O + O CSO 202A : Atoms Molecules and Photons

The Nobel Prize in Chemistry 1986

Dudley R. Yuan T Lee John C Herschbach Polanyi

"for their contributions concerning the dynamics of chemical elementary processes" CSO 202A : Atoms Molecules and Photons

Module 2 :

Ultrafast Chemical Reaction Dynamics with Ultrashort- Pulsed Lasers CSO 202A : Atoms Molecules and Photons

Consider a chemical transformation

CH3I + Na → CH3---I----Na → CH3 + NaI

Transition state

In any chemical reaction the motions of the electrons and nuclei of atoms determine how the molecules interact, and those interactions in turn create the forces that govern the reaction's dynamics.

If one can determine how molecular motions change during the critical transition phase, we can understand how new chemical bonds form and old ones disappear. CSO 202A : Atoms Molecules and Photons

Question

How can one study transition state(s) in real time?

Answer

Need ultrafast probe and detection technique CSO 202A : Atoms Molecules and Photons

Consider a simple dissociation reaction

ICN → I + CN

J. Chem. Phys., 1987, 87(4), 2395 CSO 202A : Atoms Molecules and Photons

The Nobel Prize in Chemistry 1999

Ahmed Zewail

“for his studies of the transition states of chemical reactions using femtosecond spectroscopy" CSO 202A : Atoms Molecules and Photons

Molecular structures for a reaction in progress involving two molecules (bimolecular). The diatomic iodine molecule (I2, top) is split by exchange of an electron with the ring molecule benzene (C6H6). CSO 202A : Atoms Molecules and Photons

Molecular structures for a reaction in progress involving two molecules (bimolecular). CSO 202A : Atoms Molecules and Photons

Module 3:

Catalytic Reactions on Solid Surfaces CSO 202A : Atoms Molecules and Photons

Fritz-Haber synthesis of Ammoia

Consider the reaction N2 + 3 H2 ====> 2NH3

● Simple looking reaction, Exothermic reaction ● Requires 700 K, 200 Bar pressure ● Negligible rate without a catalyst – Fe ● Fritz Haber: Nobel Prize 1918 (Discovery) ● Carl Bosch : Nobel Prize 1931 (Commercialized the Haber process) ● Elucidation of the mechanism : Gerhard Ertl: Nobel Prize 2007

Why is it such a big deal ? CSO 202A : Atoms Molecules and Photons

Greatest discovery of the last century ?? ● Ammonia production is the first stage of fertilizer preparation and the most difficult

Fritz-Haber process replicated that of N-fixing bacteria and transformed the N-cycle

Nitrogen compounds are also used in explosives – World War II CSO 202A : Atoms Molecules and Photons Nitrogen cycle

Chile Saltpeter NaNO3 : Natural source of Nitrates CSO 202A : Atoms Molecules and Photons Gerhard Ertl's Mechanism

The Physical Chemistry elements involved - Gas laws and transport processes, reaction thermodynamics, kinetics, catalysis, surface chemistry, experiments, Ultra-High vaccuum CSO 202A : Atoms Molecules and Photons

Why is this reaction so difficult ?

N2 + 3 H2 ====> 2NH3

● N – N triple bond ● One of the strongest known bonds ● The inertness of N2 is well known ● Liquid Nitrogen is frequently used to cool ● Nitrogen is easily available in the atmosphere but fixing it artificially is very hard ● Fe surface provides an easier way to break N-N bond N2 (g) ===> N2 (ads) ====> 2 N (ads) Nobel Prize in Chemistry 2007

Gerhard Ertl for his studies of chemical processes on solid surfaces CSO 202A : Atoms Molecules and Photons

Module 4: Chemistry with Supercomputers

● Consider the H2 molecule containing 2 electrons and 2 protons ● How does one calculate the equlibrium bond length of H2 ? ● Use the Born-Oppenheimer Approximation and fix protons and write Schrodinger equation

● Solve for lowest energy state and obtain E0(R) ● Vary R and find Req corresponding to minimum E0 CSO 202A : Atoms Molecules and Photons

Chemistry with Supercomputers

But the above equation cannot be solved exactly !!!

● Numerical methods implemented on a computer ● Req = 74.1 pm Bond dissociation energy = 4.52 eV

For large molecules, several bond lengths, bond angles have to be optimized !!!

● Need for advanced mathematical and numerical techniques CSO 202A : Atoms Molecules and Photons

Nobel Prize in Chemistry 1998

Walter Kohn John A Pople

The Nobel Prize in Chemistry 1998 was divided equally between Walter Kohn "for his development of the density-functional theory" and John A. Pople "for his development of computational methods in quantum chemistry" CSO 202A : Atoms Molecules and Photons

OK – That’s the structure of a single molecule, but what about dynamics ? What about behavior of a large number of molecules ?

One popular method is Molecular Dynamics Simulations using effective potential energies and classical dynamics

B. Alder and C. Wainwright (1955) and Aneesur Rahman (1959) CSO 202A : Atoms Molecules and Photons

Nobel Prize in Chemistry 2013

The Nobel Prize in Chemistry 2013 was awarded jointly to Martin Karplus, Michael Levitt and Arieh Warshel "for the development of multiscale models for complex chemical systems".