Search for nuclear quadrupole resonance in an organic quantum magnet Allen R. Majewski Department of Physics, University of Florida November 11, 2015

Theory of the nuclear quadrupole resonance spectroscopy

Theory of the nuclear quadrupole resonance Consider a single nucleus in its electronic environment … this is the electrostatic energy of a charge in fields written in terms of multipole moments. The traceless quadrupole moment tensor is the familiar expression.

Electric field gradient (EFG) V ij Quadrupole interaction energy with field. Laplace’s equation -> EFG is traceless. Choice of axes permit ordering eigenvalues of EFG by convention Cylindrical symmetry –> only one non-vanishing quadrupole moment

Only two independent parameters Assymetry parameter Cq = e 2 qQ is the “quadrupole coupling constant.” q is a measure of our ignorance.

NQR transition frequencies Hamiltonian for quadrupole interaction of nucleus with external field …matrix elements… energy levels

NQR transition frequencies NQR frequencies See more: nqr/equation.pdf

Spin 1 transition frequencies (14N) For non-axial field gradients, nitrogen has two principle transition frequencies and a third low frequency transition being the difference

Spin 3/2 transition frequencies (35Cl) For non-axial field gradients, chlorine has on transition frequency

Nuclear Quadrupole Resonance (NQR) - applications

NATO – interest in NQR NATO Science for Peace and Security Series publishes annual “Magnetic Resonance Detection of Explosives and Illicit Materials” bulletin“Magnetic Resonance Detection of Explosives and Illicit Materials” bulletin NQR employs non-invasive radio frequency methods Can penetrate luggage Is chemically specific Challenge: low sensitivity – signal to noise ratio limits practical application 2014 edition: 14 studies, 168 pages … excerpt 1 excerpt 1

14N NQR is a chemical fingerprint for explosives and narcotics The NQR signal unambiguously identifies a molecular structure Land Mine Detection - As of 29 July 2014, there were square kilometers (226.7 square miles) of Croatian territory suspected to contain land mines. These areas are located in 11 counties and 82 cities and municipalities. TSA – airport bag scanner DEA – MDMA, methamphetamine, heroine all have known NQR spectra (mail scanning?)

NQR for interesting solid state physics (non-terrorist related) NQR is extremely sensitive to electronic environment and atomic positions and local fields of a given nucleus NQR can determine chemically inequivalent sites

NQR for interesting solid state physics (non-terrorist related) NQR can characterize Structural phase transitions (by the T-dependence of NQR frequencies) Molecular motions in solids Bonding characteristics, crystal geometry Condensed matter: order/disorder properties, ferroelectric properties, affects of doping -> magnonetic transitions of quasiparticles (AFM ordering, BEC, bose glass)

My science objectives 1.Develop contemporary NQR techniques 2. Investigate interesting materials with NQR with new methodology

1. Develop NQR as a technique Increase the SNR for NQR, especially for low frequency as applied to explosives Develop methods to determine unknown NQR frequencies (this is hard) Focus on the problematic SNR at low frequencies Investigate NQR/NQR cross polarization in perovskite-types for explosives detection (uncharted territory)

2. Investigate interesting materials with NQR Complete NQR studies on interesting systems revealing new physics Complete electronic structure calculations Further existing but incomplete NQR studies using techniques developed (there are many) All the while focusing on low frequency NQR collection, furthering agenda of landmine detection (thus, an emphasis on organic metal complexes) Investigate level crossing for 14N detection with poor SRN (uncharted terriroty)

Superheterodyne Spectrometer “Most explosives contain quadrupolar nuclei (nitrogen-14) the spectral lines of which are usually located at low RF frequencies. The signal intensity in this frequency range is quite low because the low energy difference between excitation levels. Another issue is external and internal interference and spurious signals. All these problems are solved by using optimised NQR detection technique, equipment and signal processing.” NATO Science for Peace and Security Series B – “Magnetic Resonance detection of explosvies and illicit Materials” (2014)

Superheterodyne Spectrometer Perfectly phase locked:20 MHz computer clock coherent with transmit and receive functions Easy change, high quality band sensitive components Pulse sequences completely programmable 2 channel X, Y Signal averaging with real time FFT

Pulse Generator – overview nqr/superhetdetails.zip

Pulse generator - details edu/~majewski/nqr/ superhetdetails.zip

Transmitter optimizations Band pass filters Crossed diodes (never too many)

Receiver section

Generator and receiver – side by side

isolation – hybrid tee

Isolation optimization – quarter waves (double S/N)

Probe section

Probe optimizations at 30 MHz (NaClO3 control) High quality RF amplifiers Homemade IF state – TL082 + LM386 Band pass filters

NaClO3 Result NaClO3 response to a transient at MHz, pulse width=50us, signal averaging N=1000; Fourier transform (left) of discrete FID (above). res =7204 pixels; horizontal_axis=100us/div Data: nqr/tek nqr/tek Plotter scripts: nqr/scripts

Impedance matching

Impedance matching – circuit A

Motivation – Bose Glass in NiCl 2 -[SC(NH 2 ) 2 ] 4 (DTN)

RF amplifier stage – miteq fast recovery

IF (audio) amplifier stage – LM386

Labview controller - YB

Coil – large L

Probe section

Phase diagram – T < 1.2K BEC magnet journal/v489/n7416/pdf/nature pdf

Cap and coil selection

Use of density functional theory in NQR NiCl 2 - [SC(NH 2 ) 2 ] 4 dichloro-tetrakis-thiourea-nickel software.pdf

Original Plan – 35Cl in DTN Chlorine NQR typically at 25 – 42 MHz But with cubic symmetry, Cq = 0 -> no NQR With some symmetry, NQR much lower

Only two independent parameters Assymetry parameter Cq or quadrupole coupling constant ~ eq

Can we calculate the quadrupole coupling constant? Not really Density functional theory is possibility WEIN2k, CASTEP, Quantum Espresso Frozen core, pseudopotentials

Timeline In summer 2013, Tim Green (Oxford) used CASTEP to calculate EFG in DTN In fall 2013, I traveled to ETH to use Quantum Espresso to replicate calc Both predicted chlorine resonance below 10 MHz due to symmetry CASTEP-and-QE-software.pdf

See Handout for data summary Evidence for accuracy of DFT simulation: 1)CASTEP correctly predicted NQR in Sodium Chlorate as a control 2)CASTEP and QE predicted 14N NQR in DTN similar to that of known values for thiourea!! 3)CASTEP and QE widely agree, despite being completely independent software packages with-CASTEP-and-QE-software.pdf

External DTN-using-GIPAW-with-CASTEP-and-QE-software.pdf DTN-using-GIPAW-with-CASTEP-and-QE-software.pdf